Quoting reports in Spain, the report claims Barcelona sporting director Andoni Zubizarreta has switched his focus onto Luiz after Roma centre-back Marquinhos opted to join Thiago Silva at Paris St Germain.
Silva had been a top Barca target last summer, but Tito Vilanova's side lost out to PSG on that occasion as well. And they've been warned off another approach for Silva this transfer window.
Luiz was reportedly available for transfer this summer following Jose Mourinho's appointment.
He was initially reported to be part of a cash-plus-player deal for Manchester United striker Wayne Rooney - something Chelsea have strongly denied.
And Mourinho reiterated this week his desire to keep the likes of Luiz and Juan Mata at the club this summer despite the transfer speculation.
However, the report claims Zubizarreta has already made contact with Luiz's agent Giuliano Bertolucci to inform him of the club's interest.
The Spanish giants are desperate to recruit another centre-back after being forced into using emergency cover last season.
Javier Mascherano and Alex Song have both filled in at the back, as Carles Puyol and Gerard Pique have spent time on the sidelines.
A long-term replacement for Puyol in particular is a pressing concern. And having missed out on 19-year-old Marquinhos - a highly-rated prospect - and Thiago Silva - one of the world's premier defenders - they've now turned to Luiz.