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Zofia of Słuck, known in Ruthenian and Russian sources as Sophia Yurievna Olelkovich or Sophia of Slutsk, was born on 1 May 1585 in the town of Slutsk in the Grand Duchy of Lithuania, then part of the Polish–Lithuanian Commonwealth. She was the daughter of Prince Yuri (Jerzy) Olelkovich-Slutsky and Barbara Kiszka. The Olelkovich princes of Slutsk and Kopyl were a branch of the Gediminid dynasty, descending from Algirdas, Grand Duke of Lithuania, through his son Vladimir, who had ruled in Kiev. Through that Kievan connection the family also stood in the cultural and dynastic world of the Rurikid princes of Rus'. By the late sixteenth century the Slutsk line was the last surviving branch of this house, and Zofia would be its final representative.

Her father died when she was an infant, and she was left an orphan while still a child. As heiress to the Slutsk-Kopyl principality she became one of the wealthiest unmarried nobles in the Grand Duchy. The principality was among the last territorial lordships of its kind in Lithuania, carrying not only lands and revenues but also traditional rights of patronage over Orthodox churches and monasteries. Guardians administered her estates and arranged her future. In an age when the Union of Brest (1596) was drawing many Ruthenian hierarchs and nobles toward communion with Rome, the religious allegiance of the Slutsk heiress was a matter of political as well as spiritual consequence.

On 1 October 1600 she was married to Janusz Radziwiłł (1579–1620), a powerful Lithuanian magnate of the Calvinist Radziwiłł line, later cup-bearer of Lithuania and castellan of Vilnius. The marriage articles guaranteed that Zofia would remain Eastern Orthodox, that she might keep Orthodox chaplains, and that she would continue to support Orthodox institutions on her domains. She lived as a married laywoman, not as a nun, and there is no record that the couple had children. Orthodox tradition remembers her for personal austerity, generous almsgiving, and the endowment and protection of churches, monasteries, and schools of the Eastern rite at a time when such foundations were under pressure.

Zofia died on 19 March 1612, at the age of twenty-six. Having left no descendants, she was the last of the Olelkovich-Slutsk princes; her lands passed to her husband and became part of the Radziwiłł fortune. She was buried in Slutsk. Over subsequent generations Orthodox Christians in the region honored her memory as that of a righteous princess who had kept the faith of her ancestors. In 1984 the Belarusian Orthodox Church, then the exarchate of the Moscow Patriarchate, formally glorified her as a saint. Her relics are venerated in the Cathedral of the Holy Spirit in Minsk, and she is commemorated on 19 March. She is regarded in Belarusian Orthodoxy as a heavenly intercessor and a symbol of fidelity to Eastern Christianity in the former lands of the Grand Duchy of Lithuania.

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