Its administrative center was located in the urban-type settlement of Stara Syniava.

)[4] Stara Syniava Raion was located in the eastern part of Khmelnytskyi Oblast, corresponding to the modern-day boundaries of the Volhynia and Podolia historical regions.

It was first established on March 7, 1923 as part of a full-scale administrative reorganization of the Ukrainian Soviet Socialist Republic.

Stara Syniava Raion was divided in a way that followed the general administrative scheme in Ukraine.

Consequently, raions were subdivided into councils, which were the prime level of administrative division in the country.