Despite finishing the season with a winner's medal in only the Carabao Cup, De Bruyne beat out competition from four of Liverpool's Premier League title-winning squad -- Sadio Mane, Trent Alexander-Arnold, Jordan Henderson and last season's winner, Virgil van Dijk -- and City teammate Raheem Sterling to claim the honour.
In the Women's game, Manchester City's Lauren Hemp was named Young Player of the Year, while Chelsea's Beth England lifted the Women's PFA Players' Player of the Year award.
The PFA award, which is voted for by players from all four divisions in the English game, is the second individual prize handed to De Bruyne for his contribution during the 2019-20 campaign. The former Chelsea player was named last month as the Premier League Player of the Season.
Liverpool defender Alexander-Arnold, meanwhile, claimed the PFA Young Player of the Year award.
Alexander-Arnold is the first Liverpool player to be crowned Young Player of the Year since Steven Gerrard won the award in 2001.
Despite missing out on the young player honour, Manchester United forward Rashford was named as the PFA Merit Award winner following his work off the pitch in recent months aimed at helping to ensure free meals for under-privileged school children during the summer holidays.
Team of the Year:
Nick Pope (Burnley); Trent Alexander-Arnold, Virgil van Dijk, Andrew Robertson (all Liverpool), Caglar Soyuncu (Leicester City); Kevin De Bruyne, David Silva (both Manchester City), Jordan Henderson (Liverpool); Pierre-Emerick Aubameyang (Arsenal), Jamie Vardy (Leicester City), Sadio Mane (Liverpool)