With a knee injury keeping women's world number one Lindsay Davenport from joining James Blake for the U.S., the Russian duo are odds on to triumph at Perth's Burswood Dome.
While world number four Safin was only due in Western Australia on Saturday after collecting an award from the Russian government, Myskina arrived down under early in an effort to avoid a repeat of 2004 when she and Safin failed to make it through the group stage.
Safin also lost in the group stage on his only other appearance, in 2001.
"Hopefully me and Marat will do our best here because last year we lost and it was because of me most of the time," smiled Myskina, who won her first grand slam title at the French Open last year.
Myskina, one of three Russian women to win a grand slam title in 2004, said that she had set her sights on becoming world number one.
"It was a great year for me and all the Russian girls with the Fed Cup, grand slam titles and (WTA) Championship," she said. "That (world number one) is my goal for next year and if I can achieve that goal that would be great."
PERSONAL HAT-TRICK
Russia will take on Argentina, Italy and Germany in Group A of the round robin stage,
Guillermo Coria and Gisela Dulko lead Argentina's challenge, while Tommy Haas spearheads Germany's title bid after he regained his place in the world's top 20 in 2004 after more than a year out with a shoulder injury.
Meghann Shaughnessy replaces Davenport in the U.S. team as they try to win the event for a record fifth time. Blake will be hoping to complete a personal hat-trick, having teamed with Serena Williams for victory in 2003 and Davenport in 2004.
The biggest challenge to Russia, though, could come from Australia, with Mark Philippoussis and Alicia Molik carrying the hopes of the home nation.
Molik comes into 2005 as the world number 13 after the best year of her career, but much of the attention will be on Philippoussis as he returns after a two-month break, having plummeted from 10 to 109 in the rankings in 2004 on the back of 11 first-round defeats.
"I just want to start the year off strong and just enjoy myself out there," Philippoussis said.
"It was hard to enjoy the tennis (last year) and to be quite honest I didn't. I just wanted the year to end and that's why I took two months off."
Argentina take on Italy in the opening first-round match on Sunday, while Monday's action sees Russia against Germany and Australia taking on the Slovak Republic.