Polina Volfson was born in St. Petersburg, Russia. At the age of 12, she was accepted into the Kirov Theatre children's choir, with which she performed in Salambo, Othello, Nutcracker and the Queen of Spades. In 2000, Polina completed her degree of Bachelor Performance (Voice) and in 2001 attended the VCA Opera Studio. That same year she debuted in the opera Der Keiser von Atlantis bv V.Ulmann with the Geminiani Orchestra.

In 2000 she was awarded the Murray Wagg Singing Scholarship, The Sleath Lowrey Encouragement Award, and was named the Athenaeum Singer of the Year held at the VCA. In 2001 she was awarded the Mabel Kent Singing Scholarship and, in 2002, Polina won the 1st Prize at the World Festival Suoni Colori del Mondo and received Honourable Mention at the Rachmaninoff Competition in St. Petersburg.

In 2003 Polina understudied and performed Violetta in La Traviata for Melbourne Opera Company, and sang Micaela in a nationally toured production of Carmen with Adelaide based Co-Opera. She has also sung Gilda in a Melbourne City Opera production of Rigoletto. She toured Townsville and Victoria with The Three Sopranos, organised bv the Three Chinese Tenors.