The same report claims Chelsea have opened talks over a £10m deal for Roma midfielder Daniele De Rossi.
Luiz, who played in the defensive midfield position under Benitez at Stamford Bridge, is being lined up by Barcelona to add competition at the heart of their back four.
But Benitez, who was appointed Napoli boss earlier this month, is keen to hijack the move. Any move by the Italian club would be contingent on the sale of Edinson Cavani however, a player both Chelsea and Manchester City are interested in.
The Uruguayan international is valued at £52m, and Benitez would need to raise funds from the sale of Cavani to finance a move for Luiz.
Manager less Chelsea are expected to announce the return of Jose Mourinho next month, and reports have claimed the Real Madrid boss is not a fan of Luiz.
The Brazilian international is a hugely talented centre-back, but his proneness to defensive lapses led Benitez to position him in midfield rather than defence.
And the Daily Express report claims Chelsea are ready to swoop for De Rossi to play in the defensive midfield role.
The experienced Italy international is reportedly available for around £10m. He's been linked with the Premier League before, but the 29-year-old has always insisted he's committed to Roma - the club he's spent his entire career at so far.