According to the Primary Chronicle Hilarion served as a presbyter[1] in a princely residence of Berestove (today in Kiev).

He acquired the reputation of well-educated scholar and upon the death of Metropolitan Theopemptus in 1049, Hilarion was proclaimed the metropolitan of Kiev by council of local bishops on proposition of the Grand prince of Kiev Yaroslav the Wise who thus challenged the old Byzantine tradition of placing Greeks on the episcopal sees.

For his opposition, Luka was confined in the Kievan Caves Monastery for three years until his death, at which time his remains were taken back to Novgorod and buried in the Cathedral of Holy Wisdom there.

Nevertheless, Hilarion remains the best known of all the ancient Kievan metropolitans, not only because he was the first native to ascend to that position, but also because of his writings.

[1] Other archaeographers, such as Aleksey Shakhmatov, conjecture that Hilarion was one of compilers of the Ancient Chronicle Manuscript at the courtship of Yaroslav the Wise in 1030s.