Neves has signed for Al-Hilal for a transfer fee of £47m.
It is the largest transfer fee Wolves have received for a player and the biggest fee a Saudi Arabia club have paid to sign anyone.
Neves donned the Wolves jersey for six years after joining from FC Porto in the summer of 2017, helping them gain promotion to the Premier League from the Championship and consolidating their place in the top flight ever since.
The 26-year-old was made captain last season after Conor Coady joined Everton on loan.
In all, Neves made 253 appearances for Wolves and scored 30 goals, most of them spectacular long range strikes from outside the box.
Wolves sporting director Matt Hobbs told his club’s website: “Ruben is the embodiment of everything you look for when trying to bring players into a football club: a leader, a humble man and an extremely talented footballer who took Wolves to a different level.
“He was part of a great era for this club and will go down as one of our best ever players.
“We are grateful for everything he has done for Wolves and wish him and his family the very best for the future.”
In a video posted on Wolves' social media channels, Neves said: "Wolves, six seasons, 253 games, champions of the Championship, five years of Premier League football, an FA Cup semi-final, our European adventure and some huge wins."
"And thousands of memories which will last forever, what an unbelievable journey. I've worked with so many great people along the way.
"Every single moment was unforgettable."