Steve Clarke has been appointed assistant
Di Matteo has been appointed as manager by new Villa owner Dr Tony Xia who is said to be awaiting the Football League and Premier League approval for the Italian to officially take over.
The Italian is a former Chelsea, West Brom and Schalke manager, and he led the Blues to Champions League glory in 2012.
He left Bundesliga side last year Schalke after failing to qualify for the Champions League.
Steve Clarke is a former West Brom and Reading manager and was a teammate of Di Matteo during their Chelsea playing days.
He also assisted former Stamford Bridge manager Jose Mourinho at Chelsea for three years also.
New owner Dr Tony Xia was has promised funds for the new pair to combat the rigours of the Championship.
Derby County manager Nigel Pearson, and ex-Real Sociedad David Moyes were also touted for the managerial post at Villa.