A series of V2O5-TiO2 aerogel catalysts were prepared by sol-gel method with subsequent supercritical drying with CO2. Two species of surface vanadium, monomeric vanadyl and polymeric vanadates, were found in the aerogel catalysts by Raman measurements. The selective oxidation of hydrogen sulfide containing excess water and ammonia was studied over these catalysts. Aerogel catalysts showed very high conversion of H2S without emission of SO2. TPR, XRD and XPS analyses were used to reveal that the high catalytic performance of the aerogel catalysts originated from their highly dispersed VOx species and high reducibility.