System.Text.Json Serialize dictionary as array

You can do this using a JsonConverterFactory that manufactures a specific JsonConverter<T> for every dictionary type that you want to serialize as an array. Here is one such converter that works for every class that implements IDictionary<TKey, TValue>:

public class DictionaryConverterFactory : JsonConverterFactory
{
    public override bool CanConvert(Type typeToConvert)
    {
        return typeToConvert.IsClass && typeToConvert.GetDictionaryKeyValueType() != null && typeToConvert.GetConstructor(Type.EmptyTypes) != null;
    }

    public override JsonConverter CreateConverter(Type typeToConvert, JsonSerializerOptions options)
    {
        var keyValueTypes = typeToConvert.GetDictionaryKeyValueType();
        var converterType = typeof(DictionaryAsArrayConverter<,,>).MakeGenericType(typeToConvert, keyValueTypes.Value.Key, keyValueTypes.Value.Value);
        return (JsonConverter)Activator.CreateInstance(converterType);
    }
}

public class DictionaryAsArrayConverter<TKey, TValue> : DictionaryAsArrayConverter<Dictionary<TKey, TValue>, TKey, TValue>
{
}

public class DictionaryAsArrayConverter<TDictionary, TKey, TValue> : JsonConverter<TDictionary> where TDictionary : class, IDictionary<TKey, TValue>, new()
{
    struct KeyValueDTO
    {
        public TKey Key { get; set; }
        public TValue Value { get; set; }
    }

    public override TDictionary Read(ref Utf8JsonReader reader, Type typeToConvert, JsonSerializerOptions options)
    {
        var list = JsonSerializer.Deserialize<List<KeyValueDTO>>(ref reader, options);
        if (list == null)
            return null;
        var dictionary = typeToConvert == typeof(Dictionary<TKey, TValue>) ? (TDictionary)(object)new Dictionary<TKey, TValue>(list.Count) : new TDictionary();
        foreach (var pair in list)
            dictionary.Add(pair.Key, pair.Value);
        return dictionary;
    }

    public override void Write(Utf8JsonWriter writer, TDictionary value, JsonSerializerOptions options)
    {
        JsonSerializer.Serialize(writer, value.Select(p => new KeyValueDTO { Key = p.Key, Value = p.Value }), options);
    }
}

public static class TypeExtensions
{
    public static IEnumerable<Type> GetInterfacesAndSelf(this Type type)
    {
        if (type == null)
            throw new ArgumentNullException();
        if (type.IsInterface)
            return new[] { type }.Concat(type.GetInterfaces());
        else
            return type.GetInterfaces();
    }

    public static KeyValuePair<Type, Type>? GetDictionaryKeyValueType(this Type type)
    {
        KeyValuePair<Type, Type>? types = null;
        foreach (var pair in type.GetDictionaryKeyValueTypes())
        {
            if (types == null)
                types = pair;
            else
                return null;
        }
        return types;
    }

    public static IEnumerable<KeyValuePair<Type, Type>> GetDictionaryKeyValueTypes(this Type type)
    {
        foreach (Type intType in type.GetInterfacesAndSelf())
        {
            if (intType.IsGenericType
                && intType.GetGenericTypeDefinition() == typeof(IDictionary<,>))
            {
                var args = intType.GetGenericArguments();
                if (args.Length == 2)
                    yield return new KeyValuePair<Type, Type>(args[0], args[1]);
            }
        }
    }
}

Then add the factory to JsonSerializerOptions.Converters locally as follows:

var options = new JsonSerializerOptions
{
    Converters = { new DictionaryConverterFactory() },
    PropertyNamingPolicy = JsonNamingPolicy.CamelCase,
};

var json = JsonSerializer.Serialize(dictionary, options);

var dictionary2 = JsonSerializer.Deserialize<TDictionary>(json, options);

Or globally in ASP.NET Core as shown in How to set json serializer settings in asp.net core 3?:

services.AddControllers().AddJsonOptions(options =>
{
    options.JsonSerializerOptions.Converters.Add(new DictionaryConverterFactory());
    options.PropertyNamingPolicy = JsonNamingPolicy.CamelCase;
});

The underlying individual converter DictionaryAsArrayConverter<TKey, TValue> can also be used directly if you only want to serialize certain dictionary types as arrays.

Notes:

• JsonSerializer currently does not respect PropertyNamingPolicy when serializing KeyValuePair<TKey, TValue> (see Issue #1197) so I had to introduce a KeyValueDTO to get the casing "key" and "value" as required in your question.

• I did not implement a converter for non-generic IDictionary types. That could be done as an extension of the answer.

• For more on the converter factory pattern see How to write custom converters for JSON serialization in .NET : Sample factory pattern converter

• The types equivalent to DefaultContractResolver in System.Text.Json -- JsonClassInfo and JsonPropertyInfo -- are internal. There is an open enhancement Equivalent of DefaultContractResolver in System.Text.Json #42001 asking for a public equivalent.

Demo fiddle here.

If you want to keep it short and simple, you could consider projection via anonymous type:

var dictionary = new Dictionary<string, string>();
dictionary.Add("hello", "world");
dictionary.Add("how", "are you?");

var o = JsonSerializer.Serialize(dictionary.Select(x => new { key = x.Key, value = x.Value }));
// [{"key":"hello","value":"world"},{"key":"how","value":"are you?"}]

ed: of course, that's just if your feeling masochistic. If all you want is to just get the job done, just call .ToList()

JsonSerializer.Serialize(dictionary.ToList());
// [{"Key":"hello","Value":"world"},{"Key":"how","Value":"are you?"}]