The 25-year-old will work alongside Robin Armayan, who took over the top job from Jon Rudd in February.
Pavoni, who won two individual medley medals for Great Britain at the 2014 European Championships and competed at the 2012 Olympic Games, said: “I am delighted to be joining the Plymouth College swimming programme, the students, staff and facilities at the college are world-class.
“I look forward to working with the school’s athletes to produce the next crop of Olympians.”
Since retiring from the pool, Pavoni, who specialised in the 200m and 400m individual medley, has been working as Loughborough Town Swimming Club’s head coach.
Plymouth College’s director of swimming, Armayan said: “We are looking forward to welcoming Roberto to the programme, his international experience combined with his enthusiasm for the sport will be a real asset.”