Miranda joins for an undisclosed fee and has put pen to paper on a four-year deal.
A junior international with Portugal up to and including Under-20 level, the 25-year-old Portuguese centre back began his career with Benfica.
During his time with the current champions he was on loaned to Servette in Switzerland and also Deportivo La Coruna in Spain's La Liga, where he made three appearances.
The defender joined Rio Ave in the summer of 2013, where he first worked with recently appointed Wolves Head Coach Nuno Espírito Santo.
Miranda signed a long term contract with the Portuguese side and it is there he has enjoyed his most regular run of football, making 94 appearances in total, scoring four goals.
His international experience includes helping Portugal’s Under-20s to the final of the 2011 World Cup, where they were beaten 3-2 by Brazil after extra time.
Speaking after Miranda's arrival, Sporting Director Kevin Thelwell said: "Roderick's a player that we've seen many times, having had great experience at a top, top level.
"He's very good on the ball and I'm sure he'll be a great addition to Nuno Espírito Santo's squad going forward."
The 26-year-old spoke highly of the Sky Bet Championship and is looking forward to a new challenge. He said: "This is perhaps one of the best leagues in the world so to be a part of this league is a dream - I want to help Wolves to be as high as possible."
Miranda is the second new arrival at Wolves this summer, following another centre back Ryan Bennett, who arrived from Norwich as a free agent.