Football fans can download up to 50 matches from five seasons between 2002/03 and 2006/07.
Each season comprises 12 available episodes: ten 30-minute extended highlights videos and two one-hour specials -- 'Goal of the Season' and 'Review of the Season'.
Downloads cost £1.49 per episode and £9.99 for an entire season.
Classic matches available will include Arsenal's 7-0 victory over Everton in 2004/05 and the derby between Manchester City and Manchester United in 2005/06.
The Premier League has promised that more downloadable content will become available in the future.
Richard Wise, IMG Media Programme Sales senior vice-president, said: "The Barclays Premier League is arguably the greatest football league in the world and now together with iTunes the best in English football programming can be downloaded to own.
"We are especially excited that this deal is the first of its kind, giving UK iTunes users their first chance to download great football content."
Last week, speculation arose about the launch of the service. A user on Mac Forums said the following: "Don't know if I was hallucinating, but when the iTunes UK store went through its weekly update on Monday night/Tuesday morning, there was a front page link to 'Classic English Premier League Highlights'.
"The link simply took you to a prepared page [title and logo], but no content.
"However, it seems to completely disappeared now. Did anyone else see it, or should I pop down to the psychiatrist again?"
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