Team Sky's leader, who twice placed second overall in the Spanish tour, aims to correct that in this edition, starting Staurday with a team time trial in Ourense.
Froome returned from the Rio de Janeiro Games where he placed third behind Fabian Cancellara (Trek-Segafredo) in the time trial. After the Tour de France victory on July 24 and two second places in 2011 and 2014, a Vuelta win could be on the cards.
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"I've twice finished second, and I still haven't won it, and in that sense," he said, "I've definitely got unfinished business here."
Froome's Grand Tour career took off in Spain in 2011 when he started the Vuelta to support Bradley Wiggins. He out-climbed most and shined, placing second overall after three weeks behind winner Juan José Cobo and ahead of Wiggins in third.
Sky took him took him to the Tour in 2012, again to support Wiggins, where history was made. Wiggins became the first British winner and Froome placed second.
Since then, Froome has given the Tour primary focus. In 2012, after a bronze medal in the London Olympics, he placed fourth in the Vuelta.
He won the 2013 Tour and skipped the Vuelta, pulled out of the 2014 Tour after crashing to return in the Vuelta to place second behind Alberto Contador (Tinkoff).
He took his second Tour title in 2015, but crashed and quit with a broken foot bone in the Vuelta. After his third Tour title this year, he wants to takwe the top step this year in Spain.
Pressed about expanding his palmarès during the Tour, Froome said. "Times have changed. With [cycling] being so much more competitive, it's harder to stay at the top for the duration of the season when you have guys targeting and training for specific events."
Froome again will face Contador, who abandoned the Tour early due to a crash and could be fresher. Also, rivals like Colombian Esteban Chaves (Orica-BikeExchange), second in the Giro d'Italia, who skipped the Tour to rest and focus specifically on the Vuelta.
Colombian Nairo Quintana (Movistar), winner of the Giro d'Italia in 2014 and third behind Froome this year in the Tour, will also start in Ourense.
"It's no secret my condition is not the same as it was in the Tour, but I have the view of trying to get that good condition back by the second half of the Vuelta," Froome said.
"My focus for the season was the Tour, then the Olympics and I'm here on the back, of that, so I haven't trained specifically for the Vuelta. But I'm motivated."
If he wins, he would become only the third cyclist in history to win the Tour/Vuelta double and the first to do so after it moved to its late-summer date. He would join a short list that includes Jacques Anquetil, winner in 1963, and Bernard Hinault, 1978.
The Vuelta starts on Saturday with a 27.8km team time trial in Ourense.
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