When we first met Winn, she held the position of Vedek and led an arch-conservative protest against Keiko O'Brien's secular school. Although Emissary Benjamin Sisko approved, Winn objected to the scientific principles being taught about the wormhole and its aliens. She wanted Bajoran children to learn only traditional beliefs about the Celestial Temple, home of Bajor's Prophets. Winn's hidden agenda was to lure her rival Vedek Bareil to the station so that one of her followers could assassinate him. The attempt was foiled by Miles O'Brien's vigilance, but that was just the beginning of Winn's attempts to derail Bareil's bid to become the next spiritual leader of Bajor.

Vedek Winn allied herself with Minister Jaro, a provisional leader of her planet who hoped to make his position permanent through the efforts of a secret group called The Circle. Jaro used the military to take over Deep Space Nine, working to purge the Bajoran system of Starfleet outsiders. He suggested to Winn that their personal affinity could benefit them in a joint bid for power. But Winn withdrew her support of Jaro upon learning from Kira that the Cardassians, who had occupied Bajor for decades, were supplying The Circle with weapons. Jaro's coup attempt failed and he was arrested without implicating the Vedek.

Months later, Winn resurfaced to begin an investigation of Bareil on the eve of elections to choose the new Kai. Winn accused her chief competitor of having collaborated with the Cardassians during the Occupation, causing the destruction of a Bajoran Resistance cell. Kira proved her lover Bareil's innocence, yet he chose to accept responsibility rather than revealing the true collaborator -- the revered Kai Opaka, now lost in the Gamma Quadrant, who had sacrificed her own son in an effort to save thousands of other Bajorans. Bareil withdrew from the elections, leaving Winn the front-runner.

Once she gained her planet's highest spiritual title, newly-elected Kai Winn joined forces with her former rival to secure a peace treaty with the Cardassians. Sadly, Bareil was injured while traveling to Deep Space Nine to complete negotiations. Winn convinced Dr. Bashir to keep the Vedek alive for as long as she needed him, going so far as to suggest that the doctor replace Bareil's brain. But when the work was finished, Winn defended Bareil's right to die rather than live with an artificial brain. Celebrated as the architect of the peace treaty once Bareil was gone, Winn became the provisional First Minister of Bajor.

Despite her new title, Winn remained greedy for power. When former Resistance leader Shakaar opposed her in an effort to help the farmers of his province, Winn forced a military confrontation which ended in Shakaar's decision to seek the position of First Minister himself. Later on, Winn protested the Emissary's efforts to study an ancient Bajoran artifact until it led to Sisko's discovery of a fabled lost Bajoran city. Although the Kai had never trusted Deep Space Nine's captain, she came to respect his position as Emissary to the Prophets. Still, when a Pah-Wraith took over the body of Jake Sisko to fight a Prophet within the body of Kira Nerys, Winn sabotaged the conflict by illegally taking over the controls of Deep Space Nine. Afterwards Kira suggested that the Kai did not have true faith in the Prophets.

Winn's final effort to rule Bajor was triggered by Cardassian Occupation leader Gul Dukat, who pretended to be a guide sent to her by the Prophets. He became her advisor, then her lover, but when she learned that her guide's real masters were the Pah-Wraiths, Winn suffered a crisis of faith. It didn't last long. After Kira suggested that the Kai should resign, she accepted the offers of power and love held out to her by the evil ones, turning her back on the Prophets whom she felt had given her nothing.

Not even the discovery of Dukat's true identity swayed Winn from her path. She removed the forbidden text of Kosst Amojan from the Bajoran archives to learn how to free the Pah-Wraiths from the Fire Caves. Then she murdered her aide Solbor when he threatened to expose her. Ultimately, the Kai was successful in her quest to contact the Pah-Wraiths, but to her horror they chose Dukat as their vessel. Winn shifted loyalties once more, warning the Emissary to destroy the forbidden book. Enraged, Dukat sent flames to consume her just before his final confrontation with Benjamin Sisko, from which neither man returned.