Originally from the Smolensk region (whence his surname), Klim became a monk of the Zarub Monastery.
He was elected metropolitan by a synod of the hierarchy of the Rus' church under pressure from Prince Iziaslav Mstislavich.
Klim was also opposed by Prince Yuri Dolgorukiy, Iziaslav's rival, and the bishop of Novgorod the Great, Niphont.
His best-known work is Poslaniie do presvitera Khomy (Letter to Presbyter Khoma), which has survived in two manuscript forms.
It contains a symbolic explanation of the Holy Scriptures, and demonstrates his knowledge of Homer, Plato, and Aristotle.