They're just Pokeballs with a different coloration. I usually try to catch special Pokemon in Premier Balls.
Starting form Gen III if you bought 10 Pokeballs you received a Premier Ball for free, so they were pretty easy to get, but getting them is tedious since you HAVE to buy 10 Pokeballs, if you buy more you only receive the one.
There's a shop in Lumiose City that sells Pokeballs and they sell Premier Balls there.
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