The Giallorossi head into the game after the recent international break, with Pellegrini forced to withdraw from both of Italy's final two World Cup qualifiers after sustaining a slight injury in the Serie A win over AC Milan.
But after a week of rehabilitation, the midfielder is ready to take the field against the league leaders.
“We have been working very well over the last few days and the pain has gone,” Pellegrini told Sky Sport Italia. “I have returned to working with the group, and I’m available to the manager. I was disappointed not to be able to go with the national team, but it just wasn’t possible.”
Pellegrini is hoping to channel that disappointment into a fine performance at the Stadio Olimpico - and, possibly, a first goal for his boyhood club.
“I would love to score my first senior goal for the club at the Olimpico, but whenever it comes it comes,” he said. “I am always trying to get it.
“We all go out on the pitch with confidence and certainty about what we are trying to do. We are a united group. We want to continue to improve. Saturday we face an opponent competing at the top of the table. Napoli have been doing well, we have started well.
"We want to continue like this and produce a performance against Napoli before going to meet Chelsea in the Champions League.”
Pellegrini has enjoyed a fine start to life back at Roma, linking up once again with his former Sassuolo coach Eusebio Di Francesco - a man whom he credits for much of his recent development.
“The boss has always been very important to instil my mentality and approach to the game – we never can be content, we always can do more," he said. "I have a great relationship with him and all his staff.”
Now the youngster has other mentors to advise him, including club captain Daniele De Rossi.
“We talk often about things," Pellegrini revealed. "He tells me that sometimes I am a bit rash in going forward, or looking for the right ball to put my teammates through.
"Sometimes it is important to play the simple ball so you can recycle possession and breathe for a moment.”
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