The construction of the road was decreed by the Tsar two months after the conclusion of the Treaty of Nerchinsk, on 22 November 1689, but it did not start until 1730 and was not finished until the mid-19th century. Previously, Siberian transport had been mostly by river via Siberian River Routes. First Russian settlers arrived in Siberia by the Cherdyn river route which was superseded by the Babinov overland route in the late 1590s. The town of Verkhoturye in the Urals was the most eastern point of the Babinov Road.
The much longer Siberian route started in Moscow as the Vladimir Highway and passed through Murom, Kozmodemyansk, Kazan, Perm, Kungur, Yekaterinburg, Tyumen, Tobolsk, Tara, Kainsk, Tomsk, Yeniseysk and Irkutsk. After crossing Lake Baikal the road split near Verkhneudinsk. One branch continued east to Nerchinsk while the other went south to the border post of Kyakhta where it linked to camel caravans that crossed Mongolia to a Great Wall gate at Kalgan.
In the early 19th century, the route was moved to the south. From Tyumen the road proceeded through Yalutorovsk, Ishim, Omsk, Tomsk, Achinsk and Krasnoyarsk before rejoining the older route at Irkutsk. It remained a vital artery connecting Siberia with Moscow and Europe until the last decades of the 19th century, when it was superseded by the Trans-Siberian Railway and Amur Cart Road. The automobile equivalent is the Trans-Siberian Highway.
The Siberian Route was also known as the Tea Road, owing to the great quantities of tea that were transported from China to Europe through Siberia. Charles Wenyon, who passed by the "Great Post Road" in 1893, subscribed to the popular belief that "the best tea produced in China goes to Russia".
In 1915, China exported to Siberia 70,297 tons of tea, which accounted for 65% of the country's overall tea exports. The route is the namesake of the Russian Caravan blend of tea.