The world number 38 came from a set down to beat Sabine Lisicki 4-6 7-6 6-3 in two hours and 29 minutes.
Team mate Svetlana Kuznetsova became Russia's most successful player in Fed Cup history in the first match as she notched up her 27th career win in the annual competition, overcoming Julia Goerges 6-4 6-4.
Russia, who were playing without the injured world number two Maria Sharapova, can reach the Fed Cup final by winning one of Sunday's scheduled three matches.
Pavlyuchenkova's win came after Lisicki took a tight first set and then had a match point in the second as the Russian suffered serious problems with her serve before taking the tiebreak to send the match into a third set.
The 23-year-old Russian played her best tennis in the third and raced into a 4-0 lead. She suffered a brief hiccup as she tried to close out the contest but claimed victory on her third match point, sending the near capacity stadium into raptures.
"The crowd, my team and my captain were so supportive since the first point and they still kept believing in me after losing the first set," said an elated Pavlyuchenkova.
"I was struggling on my serve, but Sabine was returning really well. Of course I got a little bit nervous at the end, but I pulled it off."
Kuznetsova got a crucial break of serve in the ninth game of the first set against Goerges and continued her momentum into the second, as she moved into an early lead.
Goerges managed to get back on serve but her revival was short-lived as she dumped a forehand into the net, her 45th unforced error, to hand Kuznetsova a straight sets victory in an hour and 43 minutes.
"Playing back home is a special feeling and it was amazing," Kuznetsova said. "It was one of the best crowds I have played in front of in Russia. It was a great atmosphere and you always want to show a good game."
(Editing by Gene Cherry)
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