In 1976-1990, the city was called Gotwald (Ukrainian: Готвальд) in honor of the Czechoslovakian communist and politician Klement Gottwald.

[citation needed] The oldest settlement at the location of modern-day Zmiiv dates back to the 1st millennium BC.

The area around Zmiiv saw numerous different people groups during its history, such as the Scythians, Sarmatians, Goths, Huns, Alans, Avars, Polovtsians, Pechenegs, Tatars, and Slavs.

Igor Svyatoslavich, prince of Novgorod-Seversky, waged wars with the Polovtsy, the Zmiiv settlement founded in 1180-1185 on the Donets at the mouth of the river Mozh [uk].

[6] At the end of 17th century, the Zmiiv was already a large enough settlement, surrounded by posts: Zamost, Zidki, and Sands.

Sources also mention the weapons of the local fortress: in 1668 it had 7 large cast iron guns, 290 cores and a lot of gunpowder, with 2 shafts surrounding it and a system of underground passages.

[7] The presence of settlements in Slobozhana under the rule of the Russian tsar and the strong oppression on the part of the church and the Cossack elders did not best reflect the mood of the freedom-loving settlers.

[11] Across 1932 and 1933, 559 victims of the Holodomor genocide in Ukraine were identified in Zmiiv and neighbouring Zamostya [uk], which has since been absorbed into the city.

On 21 September 1781, the coat of arms of the city was not officially approved by the Senate of the Russian Empire and Catherine II in one day with all the coat of arms of the county cities and the provincial centre of Kharkiv and Voronezh governorships, because the Zmiiv was not then a county town.

The red box of the coat of arms depicts a "golden serpent twisting upwards and a crown worn on its head" showing the name of the city and the abundance of snakes in the vicinity.

Zmiiv is situated on the right bank of the Siverskyi Donets River at the confluence of the right-hand tributary of the Mozh [uk].

Zmiiv also has a paper mill [uk], packaging works, construction materials plant, publishing company, and some repair shops.

The station is served by a commuter rail known as elektrichka, connecting Kharkiv, Merefa, and Izium with intermediate stops.