Wolff entered the military in 1912 and transferred to the German Air Service in July of 1915. On his first flight, Wolff survived a crash that dislocated his shoulder and killed the plane's pilot. On November 5, 1916, Wolff was assigned to Jasta 11 but failed to score any victories until Manfred von Richthofen assumed command of the unit. Scoring his 9th victory on April 11, 1917, Wolff shot down a Bristol Fighter flown by Irish ace David Tidmarsh.
On May 6 , after achieving 28 victories, Wolff was given command of Jasta 29. With this unit, he scored two more victories before returning to command Jasta 11 on July 2, 1917. He was wounded nine days later, in a dogfight with 10 Naval Squadron.
When he returned to duty on September 11, 1917, he began flying one of the new Fokker Triplanes. Four days later, in another encounter with 10 Naval Squadron, Wolff was shot down by a Sopwith Camel flown by Norman McGregor.