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Canada's Frank Dancevic will take on Spain's Marcel Granollers in the second singles on Friday at the Thunderbird Sports Centre.
Spain, who lost to the Czech Republic in last year's final, are without top players Rafael Nadal, David Ferrer and Nicolas Almagro.
Nadal has been sidelined since June by a left knee injury and then a stomach complaint. Ferrer is sitting out this tie while Almagro -- who reached the quarter-finals of the Australian Open -- pulled out on Saturday because of a leg injury.
That leaves Spanish captain Alex Corretja to call upon 51st-ranked Ramos and Marcel Granollers in singles, with Granollers teaming with Marc Lopez in doubles.
Veteran Daniel Nestor will team with Vasek Pospisil in doubles for the Canadians, who are seeking to advance to the World Group quarter-finals for the first time.
The losing nation must play a World Group play-off in September to retain their spot in the top category in 2014.
Despite Spain's depleted roster, Canadian captain Martin Laurendeau said the hosts will have to be at their best to beat the five-time champions.
"We are familiar with this court and the facility now, and we know the Vancouver crowd is going to be so loud and supportive again, so we feel ready for the challenge ahead of us this weekend," he said.
"Our goal is to not just be in the World Group every year but also advance further within the World Group, so we're going to do everything we can to win."
Milos Raonic (CAN) v Albert Ramos (ESP)
Frank Dancevic (CAN) v Marcel Granollers (ESP)
Daniel Nestor/Vasek Pospisil (CAN) v Marcel Granollers/ Marc Lopez (ESP)
Milos Raonic (CAN) v Marcel Granollers (ESP)
Frank Dancevic (CAN) v Albert Ramos (ESP)