Following the title of hetmans of Poland and Lithuania, at the end of 16th century commanders of the Cossacks were also called Hetmans (or atamans).

From 1648 Bohdan Khmelnytsky uprising, Hetman was the head of the Cossack state (the Zaporozhian Host). Cossack hetmans had very broad powers and acted as heads of the Cossack state, their supreme military commanders, the top legislators (by issuing administrative decrees).
After the split of Ukraine along the Dnieper River by the Polish-Russian Treaty of Andrusovo 1667, Ukrainian Cossacks of the Hetmanate (and Cossack Hetmans) are known as Left-bank Cossacks and Right-bank Cossacks.
In Russia, the office of Cossack Hetman was abolished by Catherine II of Russia in 1764.
- Predslav Lyantskoronsky (1506–1512)
- Yevstafy Dashkevich (1506–1536)
- Dmytro Vyshnevetsky (1550–1564)
- Ivan Svirgovsky (1567–1574)
- Ivan Pidkova (1577–1578)
- Ivan Orishevsky (1579–1591)
- Bogdan Mikoshinsky (1586–1594)
- Kryshtof Kosynsky (1591–1593)
- Hryhoriy Loboda (1593–1596)
- Severyn Nalivaiko (1596)
- Petro Konashevych was a sahaidachny who led successful campaigns against the Tatars and the Turks, aided the Polish army at Moscow in 1618 and at the Battle of Khotyn in 1621. He also saw Cossack interests in the Ukrainian independence from Poland.
- Myhailo Doroshenko (1623–1628)
- Taras Fedorovych (1629–1630)
- Ivan Sulima (1630–1635)
- Bohdan Khmelnytsky (1648–1657) was the first Hetman of the Cossack Hetmanate, who is credited with winning Ukrainian independence from Poland and its incorporation into Russia.
- Ivan Bogun (June of 1651)
- Ivan Vyhovsky (1657–1659)
- Ivan Sirko (1659–1660)
- Yurii Khmelnytsky (1660–1663)
- Pavlo Teteria (1663–1665)
- Petro Doroshenko (1665–1672)
- Ivan Samoylovych (1672–1687) (Ivan Samoilovich)
- Ivan Mazepa (1687–1708) led a failed attempt to win Ukrainian independence from Russia by siding with the Swedes against Peter I of Russia.
- Ivan Skoropadsky (1708–1722)
- Pavlo Polubotok (1722–1723)
- Danylo Apostol (1727–1734)
- Kyryl Rozumovsky(1734–1764)