According to the Times, the 38-year-old who had spells at Brighton, Lincoln and Oldham, Wrexham and Grays Athletic is the surprise choice to succeed Gordon Taylor.
Molango spent three years in England’s lower leagues between 2004 and 2007 before qualifying as a lawyer.
He then spent four years as chief executive of Real Mallorca until he was sacked by the Spanish club last year.
Molango has been selected ahead of PFA chairman Ben Purkiss, who had been tipped for the role, and his appointment has raised some eyebrows within the game.
Taylor is to stand down as chief executive of the PFA by the end of this season after 40 years in the job.
The 76-year-old will end his tenure at the PFA following the completion of an internal review which has recommended a major overhaul of the players’ union.