Effective adsorption is of great importance to the photocatalytic degradation of volatile organic compounds. Herein, we succeeded in the preparation of anatase TiO2 with clean dominant {001} and {101} facets. By using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) equipped with a homemade reaction system and a coupling gas-dosing system, we found that TiO2 with dominant {001} facets exhibits higher toluene adsorption capacity than TiO2 with dominant {101} facets, which may be attributed to the different number of unsaturated 5c-Ti capable of forming the main active adsorption sites (terminal Ti-OH species). TiO2 with dominant {001} facets shows a significantly high photocatalytic degradation performance, with its degradation rate being 6 times higher than that of dominant {101} facets. Combined with simulation results, it is suggested that the synergetic effects of the formation of specific active adsorption sites, the low adsorption energy for toluene, and preservation of the free molecularly adsorbed water on the surface promote the degradation of gaseous toluene on the dominant {001} facets. This study exemplifies that the facet-dependent adsorption of volatile organic compounds is one of the most important factors to effectively engineer photocatalysts for air purification.