The world number four delayed his flight from Moscow to collect an award from the Russian government and his lack of preparation eventually told as he lost 6-3, 3-6, 6-1 to world number 18 Tommy Haas.
Anastasia Myskina had put Russia ahead with a 6-3, 6-3 win over Anna-Lena Groenefeld but Haas and Groenefeld, who only met for the first time three days ago, beat the Russian pair in the deciding mixed doubles, winning the match tiebreak 10-6 to clinch victory in their Group A tie.
Given that he had less than 24 hours to prepare for his match, Safin produced a commendable performance, recovering well from the loss of the first set to force a decider.
But Haas, who arrived in Perth on Friday, always looked the fresher and an early break in the third set put him on his way to victory, levelling up the tie at 1-1.
"It is a good excuse," said Safin of his late arrival.
"I tried my best but unfortunately in the third set he was much better than me. I had no strength and almost fell over a couple of times, but I was trying."
STRONG COMEBACK
Haas was coming off a strong comeback year which saw him climb back up the rankings having only returned to the tour in February after 14 months out following shoulder surgery.
"I think he (Safin) had a little bit of an off-season and didn't have as much time to prepare, but I am pleased with my win," Haas said.
Myskina, who became the first Russian woman to win a grand slam title when she won at Roland Garros in June, breezed past Groenefeld in 62 minutes.
And when Safin and Myskina hit back from the loss of the first set of the mixed doubles to level it up, it looked like they would go on to clinch the rubber, but the Germans held on to win it 10-6 and upset the top seeds.
In the opening match of the day, Mark Philippoussis was easily beaten on his first outing of the year but Australia still scrambled to a 2-1 victory over Slovakia in Group B.
After Alicia Molik defeated Daniela Hantuchova 6-3, 6-3, Philippoussis, who plummeted to 109 in the world rankings in 2004, went down 7-5, 6-2 to Dominik Hrbaty.
Molik then outshone partner Philippoussis in the deciding mixed doubles to help Australia wrap it up 6-7, 6-3 and 11-9 in the match tiebreak.
"It was a little ugly, but a win's a win," a relieved Philippoussis said.
"I have been practising well but there's nothing like match practice and the confidence wasn't there and I was a tense.
"Hopefully, I'll improve with every match and maybe some of Alicia's confidence will rub off on me."
The United States begin the defence of their title on Tuesday with a Group B clash against the Netherlands, while Germany are back in action against Italy.
