Milos Raonic leads Canada into the World Group semifinal tie Sept. 13-15 on clay at the Belgrade Arena. The winning country moves onto the final in November against the winner of the other semifinal between Argentina and Czech Republic.
Canada has never made it this far in the international men's team tennis event that begins each year with 130 countries. Only 16 qualify for the World Group each year. Each tie consists of four singles matches and a doubles match.
"As a group we've gone through events and moments that are pretty uplifting and it's been a year where we've done a lot of things we've never done before and we want to continue to do that," Canada's captain Martin Larendeau said Tuesday during a conference call.
"We're really looking forward to the challenge and the chance to keep alive this great story we're going through."
Raonic, from Thornhill, Ont., is the highest-ranked male singles player in Canadian history at No. 11 in the world. He reached his first Masters final at last month's Rogers Cup in Montreal where he lost in straight sets to current world No. 2 Rafael Nadal of Spain.
Raonic, 22, advanced to the fourth round of the U.S. Open before falling in five sets to Richard Gasquet of France on Monday.
Djokovic is 3-0 in Davis Cup singles in 2013. He and Raonic have never met on the professional tour.
Frank Dancevic of Niagara Falls, Ont., doubles specialist Daniel Nestor of Toronto and Vancouver's Vasek Pospisil round out the Canadian squad.
Ottawa's Jesse Levine, Filip Peliwo of Vancouver and Toronto's Adil Shamasdin will also travel to Belgrade as part of an extended squad of players.
Serbia's Janko Tipsarevic is ranked No. 21 in men's singles and reached the third round of the U.S. Open.
Nenad Zimonjic, the No. 1 doubles player in the world in 2008, and Dusan Lajovic will also represent Serbia with Bogdan Obradovic as the team's captain.
The Canadians will fly to Belgrade later this week. They'll practise on clay courts in the city and start training on the competition surface Monday, Laurendeau said.
"It'll be a challenging surface to adapt to for both teams," he said. "The Serbs have also been playing on hard courts ever since Wimbledon and there's not much time to turn it around.
"We also know that we're playing indoors. Indoor tennis is always something we enjoy and we like. Even though it's clay, we still play in conditions where the ball will travel pretty well."
"At least that's something we look forward to and we'll see how the court is laid down when we go for practice on Monday morning."
Dancevic, 28, has been a Davis Cup regular for Canada since 2002. His three-set victory over Marcel Granollers gave Canada a 2-0 lead after the first day of February's tie against Spain.
A back injury sidelined him for April's quarter-final against Italy, but Dancevic qualified for the U.S. Open main draw and reached the second round for the first time in his career last week.
Pospisil, 23, is blazing a trail in singles this summer. He lost to Raonic in an all-Canadian semifinal at the Rogers Cup, which launched him into the top 40 in the world rankings. He has already begun hitting on clay in Florida in preparation for the Davis Cup, Laurendeau said.
Nestor and Pospisil reached the third round of the U.S. Open in their first Grand Slam together as a doubles team. Nestor, 40, is Canada's most decorated tennis player having won doubles titles in all four Grand Slams during his career, as well as an Olympic gold medal in 2000.
Laurendeau wasn't showing his hand on whether Pospisil or Dancevic will be his No. 2 singles player.
"The first thing is to go over there and see how everybody feels," he said. "They've got nine months of tennis in their bodies and we have to evaluate and make sure everyone is fit to go through this long weekend and be fit the play to four- or five-hour match.
"We can't jump the gun too quick. We'll have to assess when we get there."
Canada and Serbia will meet for the first time in Davis Cup competition. Serbia won their first World Group tie in 2010 en route to becoming the Davis Cup champion that year.
Serbia is currently ranked third in the International Tennis Federation rankings of Davis Cup countries, while Canada is No. 7.
"We had better ranked teams ahead of us when we took on Spain and Italy and we did well," Larendeau pointed out. "We're going in with the same perspective.
"Regardless on the rankings, Davis Cup is always tough conditions especially abroad. Whether we play the world No. 1 or the world number whatever, it's always a match that we try to prepare the best for and we give it all we have."