The former Salford forward, who has spent the last 14 years of his life trying to establish rugby league in his homeland, believes an Italian team in Super League could be just the catalyst for it to take off.
He also believes it presents an opportunity for officials to strengthen the original concept of Super League Europe by spreading the game outwards from England and France.
"There is a definite chance of a good Super League franchise happening over there," Napolitano said. "It's massive.
"As soon as the fans come to watch rugby league, they really enjoy it.
"I've heard the RFL - and I won't mention any names because it's not fair - have turned around and said they don't think it will be well supported and they don't think it will be successful.
"But how can you make that judgement without making a feasibility study?
"I'm not just a coach, I've worked in administration and development.
"I know Italians pretty well and, if you are successful, they will follow.
"There is no doubt we'd need stipulations like the Catalans did but if they're genuine about a European Super League, let's be true about it."
Napolitano, who was born in Salford but now lives and works in Sydney, is a director of the Italian Rugby League Federation which has recently opened talks with their rugby union counterparts in a bid to map a way forward for both codes.
Italian rugby union has made rapid strides since their country was admitted to the Six Nations and Napolitano believes there is a blueprint there to follow.
"Rugby union is very strong in Italy but there is no reason why we can't co-exist and talks are now happening," he said.
"We've got an absolutely great platform where we have two federations that are talking to each other.
"We understand that we are different sports but we can work together. If we can do that, we can also assist the rugby union.
"It's quite common knowledge that there is a lot of rugby league influence now in rugby union and we wouldn't want that any different.
"Some players are born to play rugby union and some players are born to play rugby league.
"Some cross over every now and then but, at the end of the day, if we can have a strong nation playing rugby in Italy, whether it's union or league, there is a margin there where they can both be successful. I truly believe that."
Under Napolitano's coaching, the Azzurri have made a big impression on the international stage, following up their stunning win over England with a World Cup victory over Wales and a draw with quarter-finalists Scotland.
Napolitano has no doubt his team would have fared even better had he been able to select first-choice half-backs Craig Gower and Terry Campese, who were both late withdrawals.
He is now uncertain when Italy's next game will be but is hoping an anticipated profit from the World Cup will be ploughed into the international game to the benefit of the smaller nations.
"The World Cup is not just about a competition every four years," Napolitano said. "We've got to be increasing international presence in these domestic countries."