Rabbi Zev Wolf Kitzes was born around 1695, the son of Rabbi Yitzchak and Esther. Renowned for his learning in every part of the Torah and in other sciences, he was rabbi of the Tulchyn community and later moved to Medzhybizh, where his father-in-law, Rabbi Naftali, was rabbi. There, with Rabbi David Purkes, he led the circle of "chassidim", ascetics who preceded the Baal Shem Tov. When the Baal Shem Tov arrived in Medzhybizh, the two at first opposed him, before recognising his greatness and becoming his closest disciples.

According to Rabbi Yitzchak Alfasi, he was the Baal Shem Tov's right hand and even lived in his house; he represented him several times in disputes with the opponents. The Baal Shem Tov once told him: "Between you and me there is only a hair's breadth, but that hair you will never be able to cross." He was famous for his piety and meticulous observance of the mitzvot.

He served as baal tokea, the one who sounds the shofar on Rosh Hashanah, in the Baal Shem Tov's beit midrash. According to a famous Chassidic story, the Baal Shem Tov taught him the kavanot of the shofar, which he wrote down on a sheet. When the time came to blow, he found he had lost it and had to sound the shofar with a broken heart, without the intentions. The Baal Shem Tov later explained that a broken heart opens every door, like a master key that opens all the locks of the King's palace.

He passed away on 12 Cheshvan 5549 (1788) and was buried in the Baal Shem Tov's ohel in Medzhybizh.