Matviyenko was born on 10 October 1947 in village of Nedilyshche, Yemilchyne Raion, Zhytomyr Oblast at the time in the Ukrainian SSR in the Soviet Union (today - Ukraine). She completed her studies in Ukrainian philology at the Kiev University in 1975. In 1968 she entered the vocal studio of the Ukrainian State Folk Choir named after Hryhory Veriovka and soon became a soloist. In 1988 she received the Shevchenko National Prize, a Ukrainian State prize named after Taras Shevchenko.
Her repertoire includes numerous Ukrainian folk songs. Nina is the first performer of works by the composers Yevhen Stankovych, Myroslav Skoryk, Iryna Kyrylina, Hanna Havrylets and many others. She has performed on television in numerous films and on radio.
From 1966-1991 she was a soloist of the Ukrainian State Folk Choir. From 1968 a member of the folk trio "Zoloti kliuchi". In recent times she has been performing with the Kiev camerata orchestra, and the Kostyantyn Chechenya Early Music Ensemble.