Russia boasts seven WTA Top 100 players, including world No. 5 Maria Sharapova, but injuries and other commitments had left the four-time Fed Cup champion and last year's runner-up looking down the rankings for players.
Russian captain Anastasia Myskina installed Khromacheva into the leadoff spot against Australia's Casey Dellacqua for the first of Saturday two singles matches and has Kudermetova in the second match versus Samantha Stosur.
The singles players switch opponents for Sunday, with Stosur taking on Khromacheva in the opener and Dellacqua playing Kudermetova. The best-of-five series is to conclude with Dellacqua and Ashleigh Barty teaming for a doubles match against Victoria Kan and Valeria Solovyea.
Khromacheva, 18, is No. 241 in the WTA rankings and is 0-2 in Fed Cup play. Kudermetova, 16, is ranked No. 650 as she heads into her Fed Cup debut. By comparison, Stosur, 29, is 16th in the rankings and 25-11 in Fed Cup singles matches. The 25 wins is the Australian Fed Cup record. Dellacqua, 28, is ranked 80th and has an 11-5 overall Fed Cup record.
That makes Russia, which lost in the Fed Cup finals to Italy last year, a long shot to win the series and gain a spot in the Fed Cup semifinals. The Australia-Russia winner is to take on the winner of a series between Germany and the Slovak Republic in April.
All of Russia Fed Cup titles and two of its six second-place finishes have come since 2004. Australia is second (tied with the Czech Republic) with seven Fed Cup titles but the Australians haven't won the event since 1974 and last made the finals in 1993.