The 40-year-old, who is currently a free agent after leaving Portuguese second-tier club Chaves before the tournament, will travel to Chile in the coming days to complete a medical before the transfer is officially confirmed.
Colo Colo president Anibal Mosa announced the deal ahead of the club's league match against Deportes Limache.
"Vozinha will be a Colo Colo player. In the coming days he will travel to Chile, undergo the usual medical examinations and then be presented here at the Estadio Monumental," Mosa said.
Vozinha became one of the biggest surprise stars of the World Cup as he helped tournament debutants Cape Verde produce a series of memorable displays.
The experienced goalkeeper played a key role in Cape Verde's goalless draw against eventual champions Spain during the group stage before producing another impressive performance as his side pushed eventual runners-up Argentina into extra time in the last 32.
His displays earned him a place in FIFA's fan-selected World Cup Dream Team and attracted interest from clubs after the tournament.
Mosa said Vozinha had fully deserved the opportunity to join Colo Colo following his performances on football's biggest stage. He also admitted the signing would generate excitement and interest around the club.
Although the transfer has not yet been officially completed, Colo Colo have already hinted at the arrival of the veteran goalkeeper by posting an image on social media that appeared to feature his trademark curly hair.
If he passes his medical, Vozinha will be unveiled at the Estadio Monumental as Colo Colo add one of the World Cup's most inspiring success stories to their squad.
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