Pavlyuchenkova, the world No 22, assumes the mantle of Russian No 1 this weekend despite not being the highest ranked player in the side, with Maria Sharapova and Vera Zvonareva both out injured.
Jankovic, meanwhile, is a seasoned Fed Cup veteran with 28 ties and a 32-12 win-loss record under her belt.
"We made the Fed Cup semi-final for the first time in history," Jankovic said. And this match in Moscow will be a historic moment for us. Hopefully we can make it to the final."
"The Fed Cup is a very special tournament. It's team work, playing for your country ... and to represent your country in the best possible way is my job and a huge responsibility."
Saturday's second rubber sees two former Grand Slam champions, Russia's Svetlana Kuznetsova and Serbia's Ana Ivanovic, go head-to-head.
On Sunday, the reverse singles rubbers will be followed by a potentially crucial doubles rubber. The named pairs at the moment are Kirilenko and Elina Vesnina for Russia and Bojana Jovanovski and Aleksandra Krunic for Serbia who are appearing at this stage of the competition for the first time.
Meanwhile, holders the Czech Republic will have Lucie Safarova bidding to avenge a defeat by Francesca Schiavone in the 2010 semis when she takes on the Italian No 1 in the opening rubber of their tie against Italy on Ostrava.
The defending Fed Cup champions will also be looking for revenge this weekend having been outplayed 5-0 by their visitors when the two teams last met in Rome on clay.
The home team are led by Wimbledon champion Petra Kvitova, who faces Sara Errani in Saturday's second rubber.