The former UK foreign secretary has quit the Stadium of Light after the Italian's arrival as Martin O'Neill's replacement citing his "past political statements" as his reason
The former foreign secretary, who has also been a non-executive director at the Stadium of Light since February 2011, announced his decision on his personal website.
"I wish Sunderland AFC all success in the future," he said. "It is a great institution that does a huge amount for the North East and I wish the team very well over the next vital seven games.
"However, in the light of the new manager’s past political statements, I think it right to step down."
The volatile Italian, who has no top-flight experience after only managing with Swindon Town in League One and League Two, has been tasked with saving Sunderland from relegation after their 1-0 defeat to Manchester United left them only one point above the drop zone.
That defeat, Sunderland's eighth game without a win, cost Martin O'Neill his job as manager and the onus now falls on the controversial Di Canio, 44, to preserve the Black Cats' Premier League status.
Di Canio has previously discussed his political views, saying: "I am a fascist, not a racist," in response to the controversy surrounding his raised arm salute when playing for Lazio.
After resigning as Swindon boss in February, where the former Celtic, Sheffield Wednesday, West Ham and Lazio player led them to promotion from League Two, Di Canio was linked with the vacant Reading job which was eventually given to Nigel Adkins.