Chaves triumphed in 4 hours 16min 10sec having broke away with six kilometres of the 169km stage from Caltanissetta to Mount Etna remaining. 

He came together at the end with Yates, who attacked from the select peloton of overall contenders in the last two kilometres and indicated to Chaves to take the win.

Yates now leads with an overall time of 22:46:3.0, giving him a 16-second advantage over nearest challenger and reigning champion Tom Dumoulin of Team Sunweb. 

Chaves has moved up to third position and is 26 seconds back.

Team Sky’s Chris Froome, who is bidding to make history as only the third man to win three of cycling's Grand Tours in a row, finds himself in eighth spot.

He is 1:10.0 behind fellow Briton Yates having crossed the line 26 seconds back in the second group along with the likes of Dutchman Dumoulin and France’s Thibaut Pinot of Groupama-FDJ.

"It was a great day for us," Chaves was reported as saying by Cycling News.

"I went for it after a lot of attacks, and then we won the stage and got pink jersey."

He added: "It's fantastic.

"I can only thank Simon for letting me win the stage.

"Things like that don't happen every day."

Yates, only the fourth Briton to wear the pink jersey in the Giro d'Italia after Mark Cavendish, Bradley Wiggins and David Millar, said: "It's a special feeling and special to do it with this guy (Chaves).

"We've kind of grown up together and this is the final result."

Australia’s Rohan Dennis of BMC Racing Team had held a one-second lead going into the stage, but he fell away and was unable to keep the pink jersey.

Dennis dropped to sixth place overall, 53 seconds behind Yates.

The Giro d'Italia is due to continue tomorrow.

Stage seven is a 159km ride from Pizzo to Praia a Mare.