Zoe was one of the few Byzantine empresses who was Porphyrogenita, or "born into the purple" (that is, as the child of a reigning emperor). She was the daughter of Constantine VIII and Helena, daughter of Alypius. Her father had become co-emperor in 962, and sole emperor in 1025. He reigned for only three years between December 15, 1025 and November 15, 1028.
Worried by the prospect of associating another man with the imperial house, Constantine VIII prevented his daughters from marrying until the very end of his life. Before dying, Constantine had married Zoe to his chosen heir Romanos III Argyros, the prefect (eparch) of Constantinople, on November 12, 1028. By this time, Zoe had reached 50 and had failed to produce any heir. Romanos III succeeded to the throne together with Zoe three days after they married, but this failure helped alienate the couple. Romanos incurred his wife's animosity by paying little attention to her and limiting her spending, while Zoe herself became enamoured of her courtier Michael.
On April 11, 1034, Romanos III was found dead in his bath, and there was speculation that Zoe and Michael had had him strangled or drowned. Zoe married Michael later the same day, and he reigned as Michael IV until his death in 1041. Although Michael proved to be a more uxorious husband than Romanos, Zoe remained excluded from politics by the monopoly on government enjoyed by Michael's brother John the Eunuch. The disgruntled empress conspired in vain against John in 1037 or 1038.
Shortly before the death of Michael IV in December 1041, the couple adopted as their son Michael V, the son of Michael IV's sister. After several months of rule, the new emperor exiled his adoptive mother to a convent on Principus (one of the Princes' Islands near Constantinople). The population of the city, loyal to Zoe, quickly forced him to recall the empress and her younger sister Theodora in April 1042. The sisters deposed Michael V, blinded him, and exiled him to a monastery, where he died later the same year. For two months, Zoe shared power with Theodora, until she could find yet another husband, her third, and the last she was permitted according to the rules of the Orthodox Church. Her choice was Constantine IX Monomachos (reigned 1042–1055), who outlived her by four years. Zoe died in 1050.
Zoe was fifty when she first married. Despite her age, she married twice more. Ironically, the most capable of her husbands was the one who was least well prepared to be emperor, Michael IV. It is said she was stunningly beautiful, and one writer even commented that, like a well baked chicken, "every part of her was firm and in good condition." She was aware of her charms and meant to keep and use them for as long as possible. With typical Byzantine ingenuity, she had many rooms in her chambers converted into laboratories for the preparation of secret ointments, and she was able to keep her face free of wrinkles until she was sixty.