The Premier league governing body will probed following a complaint from Virgin Media, which said more matches should be available for live broadcast.
Ofcom said: "Virgin Media argues that the proportion of matches made available for live television broadcast under the current Premier League rights deals - at 41% - is lower than some other leading European leagues, where more matches are available for live television broadcast."
Virgin argues that this "contributes to higher prices for consumers of pay TV packages that include premium sport channels and for the pay TV retailers of premium sports channels".
Tom Mockridge, Virgin Media's chief executive, called Ofcom's investigation "welcome news".
"The fact remains that fans in the UK pay the highest prices in Europe to watch the least amount of football on TV. Now is the right time to look again at the way live rights are sold to make football even more accessible," he said.
"We look forward to working constructively with the Premier League, the wider industry and Ofcom to ensure a better deal for football fans."
In reply, the Premier League said: "We note that Ofcom has launched an inquiry. Ofcom has stated that this is at an early stage and it has not reached a view as to whether there is sufficient evidence of any infringement.
"The Premier League currently sells its audio-visual rights in a way that is compatible with UK and EU competition law and will continue to do so."