Separate and joint work of photocatalytic oxidation based on TiO2 and surface barrier discharge as a source of active oxygen and UV radiation is investigated for acetone vapors destruction under ambient air conditions. Experiments were carried out in a 404 l airtight Plexiglas chamber and used five different combinations of photocatalyst, barrier discharge and ultraviolet irradiation under identical initial concentration (similar to 170 ppm) of acetone. It is shown for the synergistic action of photocatalytic method and barrier discharge that the initial rate of acetone decomposition per watt of input power increases in more than 1.5 times compared to photocatalytic oxidation. Under operation of plasma of barrier discharge, intermediate products are formed such as CO, acetic acid, acetaldehyde and methane nitrate (CH3NO3). These products are not detected for photocatalytic oxidation. Some interesting features of kinetics of acetone decomposition and formation of intermediate products with participation of barrier discharge are revealed.