Fermentation of Stolichnaya starts with wheat and rye grains and artesial water from the Russian city of Samara and the Kaliningrad region. The fermentation takes about 60 hours. Once fermentation is complete the resulting liquid is distilled four times to a strength of 96.4% ABV. This spirit is then diluted to bottling strength with more artesial well water. It is then filtered through quartz, sand, activated charcoal, and finally through woven cloth.

The brand's logo features the words "Stolichnaya vodka" in gold cursive script, over a drawing of a Moscow landmark currently under re-construction, the Hotel Moskva, where Stalin once stayed and the site of one of the first Metro stations in the capital city. ("Stolichnaya" is the adjectival form of "stolitsa" ["столица"], meaning "capital city".)

Stolichnaya has its origins in the Moscow State Wine Warehouse No. 1 which was opened in 1901 by the authorities to ensure higher quality vodka production.

There's a confusion about the actual birth date of Stolichnaya vodka. The earliest confirmed production date is 1948, but the label design clearly predates 1946. It is likely that it was created by V. G. Svirida around 1944. However, there is a trademark patent dated 1938, which is sometimes quoted as another birth date.

In 1953, Stolichnaya was introduced on the international trade show in Bern and received a gold medal.

The Stolichnaya label no longer makes reference to Russia or Russian Vodka, as displayed on the label in this article. Stoli is now produced and bottled in Latvia for SPI Cyprus and is labeled as Imported Premium Vodka.