Vollers studied Protestant theology and Oriental languages in Tübingen, Halle, Berlin, and Strassburg.
His first professional appointment as teacher at a local gymnasium (high-school) in Fürstenwalde in Saxony, where he served between October 1881 to 1882.
After the defense of his PhD thesis at Halle University he was appointed assistant at the Royal Library in Berlin in October 1882 under the directorship of Carl Lepsius.
In 1886, he was appointed director of the Khedival Library in Cairo, a position held by several German orientalists before World War I.
After disputes which became personal over his book Volksprache und Schriftsprache im alten Arabien (1906), Vollers left the Deutsche Morgenländische Gesellschaft in 1908.