The Sunderland manager, who made 26 appearances for Uruguay, feels the South Americans will be too strong for Roy Hodgson's men in June's Group D meeting.
Friday's draw pitched the two nations alongside Italy and Costa Rica, with Uruguay the seeded team, despite having required a play-off to qualify.
And Poyet believes his countrymen, who boast the likes of Luis Suarez, Edinson Cavani and Diego Forlan, will prevail against the nation where he has long plied his trade as a player and coach.
"If I had to choose between the two, I'd put my money on Uruguay - and that's not because I'm biased," he said in quotes reported by The Daily Star.
"The group of players have been together for quite a while now and they're strong.
"They say in England, you're only as good as your two strikers and when you've got Luis Suarez and Edinson Cavani, you've always got a chance.
"Uruguay have a good system and are very difficult to play against. They have a way they play, good commitment and two great strikers."
