Valdivia played in three of Chile's four games in their run to the last 16 of the World Cup, scoring in the 3-1 opening win over Australia, but announced the end of his international career four days after the conclusion of the tournament in Brazil.
However, the Palmeiras man has since backtracked on his decision and has been called into the squad for Friday's friendly as Copa America hosts Chile continue to build towards next year's competition.
Jorge Sampaoli's decision to recall Valdivia came at the request of Arsenal star Alexis Sanchez who, after the 2-2 draw with Bolivia last month, stressed that he need an attacking midfielder to link up with.
Valdivia was reportedly welcomed back to training by his team-mates with a large ovation on Tuesday - and captain Claudio Bravo has been quick to underline the importance of the 31-year-old playmaker.
"It's important because Jorge brings us a lot," Barcelona goalkeeper Bravo said. "He is very talented and able to help us a lot on the pitch.
"He is also a major player in the dressing room with lots of experience and brings a lot more than a young player."
While much of the focus at Estadio Regional Calvo y Bascunan will be on Valdivia's return against the country of his birth, defender Igor Lichnovsky is in line to win his first senior cap.
The centre-back captained the Chile Under-20 side that reached the quarter-finals of last year's World Cup and joined Portuguese giants Porto from Universidad de Chile in June.
Lichnovsky has yet to feature for Porto's first team, but that has not stopped Sampaoli from selecting the 20-year-old to potentially face a side that heads into the game with head coach Noel Sanvicente still searching for his first win as boss.
After taking over in September, Sanvicente was given an illustration of the task ahead of him as Venezuela slumped to a 3-1 defeat at the hands of South Korea in his first game in charge, although they immediately produced an improved performance in the 2-2 draw with Japan four days later.
Now Venezuela will attempt to win their first game since September last year - a 3-2 World Cup qualifying victory over Peru - but will have to do so without striker Salomon Rondon, who has been left out of the squad after being sent off in the loss in Bucheon.
Midfielder Juan Arango returns as captain after 17 months away from the national set-up, but Sanvicente is well aware of the threat posed by Chile.
"The idea is to make Arango feel comfortable in this new process," Sanvicente said. "We must take advantage of his experience.
"Chile is a very tough opponent. If we give them space they are very dangerous. The idea is not to defend the entire game, we must go out there and be bold."
