Rahel Yanait Ben Zvi was born in the Ukraine. Even before moving to Eretz Yisrael, she aligned herself with the labor movement and worked to establish chapters of Poalei Zion in Russia. She was educated in Russia and later in France, studying agronomy.

Ben Zvi arrived in Eretz Yisrael in 1908, and became a leader of HaShomer, whose members were largely affiliated with the Poalei Zion, and later, T’nuot HaPo’alot, a women's labor movement. She served on the editorial board of "Ha-Ahdut," the Hebrew newspaper of Poalei Zion, and following World War I, she became a founder of Ahdut Ha-Avodah Labor Party.

Ben Zvi's activism also emerged during the wars. In World War I she volunteered for the British, and kept contacts between HaShomer and the Nili group. Before the establishment of the State, she was a leader of the Haganah in Jerusalem.

Ben Zvi contributed notably to the field of education, helping to found and teaching at the Hebrew Gymnasium in Jerusalem, the second modern high school in the country, and later establishing an agricultural high school for girls near Talpiot, Jerusalem. Shortly after the establishment of the State, the agricultural youth village at Ein Kerem was launched, largely through her efforts.

In 1918, she married Yizhak Ben Zvi, whom she had known through her activities with Poalei Zion, HaShomer, and "Ha-Ahdut." When, in 1952, her husband became the second president of Israel, she assisted him in his official duties and worked with him to make the president's house a landmark central to all Israelis. Following her husband's death in 1963, Ben Zvi became an active member of Yad Ben Zvi, the historical and research institute named for her husband.

With her husband, Ben Zvi wrote Eli, a book about the son they lost in the War of Independence. She later published her own memoirs, and following her husband's death, helped to edit his scholarly writings. For her special contribution to the State and to Israeli society, Ben Zvi was awarded the Israel Prize in 1978.