#JavaScript (ES6), 73 54 50 bytes
JavaScript (ES6), 73 54 50 bytes
(Saved some bytes thanks to @LeakyNun, the edited challenge, and @CraigAyre.)
s=>s.match(/../g).map((c,i)=>('0x'+c)/(i-3?1:255))
let f=
s=>s.match(/../g).map((c,i)=>('0x'+c)/(i-3?1:255))
console.log(f('00ff0080'));