The former Manchester United defender got the nod from a shortlist of 15 players, following an online public vote and input from the Premier League Awards Panel.
Five other ex-Reds were in that group - Michael Carrick, Andy Cole, Gary Neville, Michael Owen and Rio's regular centre-back partner Nemanja Vidic.
Sir Alex Ferguson and Arsene Wenger were also inducted recently, with other United representation already in place in the shape of Eric Cantona, David Beckham, Roy Keane (all in 2021), plus Paul Scholes, Peter Schmeichel and Wayne Rooney (a year later).
Rio won six Premier League titles with Sir Alex's men, after joining from Leeds United for a British transfer record fee in 2002, the most recent of which came in the legendary manager's final campaign in charge.