champions and the Serbs are the top seeds.
Ivanovic, a former no 1 who is currently ranked 17th, won the 2008 French Open, while the third-ranked Djokovic won the Australian Open the same year.
Indeed, there have been few teams that have boasted two Grand Slam winners in the 22-year history of the event, so it is not surprising that the Serbs are odds-on to claim the diamond-encrusted tennis balls handed to the winners of the final on January 8.
The pair can also call on some experience under the unusual mixed teams format, which sees teams broken up into two groups of four for the round robin stage, with the teams that top each group meeting in the final.
Ivanovic and Djokovic played together here in 2006, when they finished second in their group, with Djokovic losing two of his three singles matches and Ivanovic winning two of her singles encounters.
Djokovic teamed up with Jelena Jankovic the following year, reaching the final but losing to the United States team of Serena Williams and Mardy Fish.
Ivanovic said on Thursday she was looking forward to teaming up with Djokovic again, the pair having known each other since before they were tennis stars.
"Novak has been asking to me come back every since the first year we played here," she said.
"I am really excited about the possibility of getting further this time and it is a great event to start the year.
"There are lots of great players and it is a good field."
However, the pair are not the only big winners in the event.
Belgian former world No.1 Justine Henin, a seven-time Grand Slam champion, is launching her latest comeback here and will team up with Ruben Bemelmans.
Henin is resuming after a six-month layoff with an elbow injury and the Belgians face the host nation pairing of Alicia Molik and dual Grand Slam champion Lleyton Hewitt in the opening tie of the tournament on Saturday.
The 28-year-old Henin welcomed the chance to play former world No.8 Molik, herself on the comeback trail after retirement, in the women's singles rubber and said it was a great way to start her 2011.
"Playing Australia in the first match is a dream for us and it is going to be a fantastic atmosphere, so I am very much looking forward to it," Henin said.
Francesca Schiavone, a shock winner at this year's French Open, teams up with Potito Starace to represent Italy.
American champion Serena Williams was a late withdrawal from the event, her place in the American team taken by the colourful Bethanie Mattek-Sands.
She will partner the towering John Isner against the French team of Kristina Mladenovic and Nicolas Mahut in their opening tie on Monday.
That pits Isner and Mahut against each other for the first time since they played the longest match in tennis history at this year's Wimbledon, with the American winning 70-68 in the fifth set.