It is very essential to improve the activity and selectivity of photothermocatalysis (PTC) by tailoring the microstructures of photothermocatalytic materials. Herein, we exploit a facetheterojunction strategy to fabricate photothermocatalysts, by which CdSÀ Au-{001}BiOCl{110}-MnO x is constructed by respectively depositing CdSÀ Au on the {001} facets and MnO x on {110} facets of BiOCl nanosheets. This material exhibits excellent activity for toluene oxidation and near 100 % selectivity from toluene to carbon dioxide under full-spectrum sunlight irradi-ation. The conversion rate of toluene under PTC condition is significantly enhanced by 47.5, 1.8 and 1.7 times compared with that of sole PC, TC and the sum of TC and PC. There is a synergistic effect between photocatalysis and thermocatalysis, in which the S-scheme photocatalyst CdSÀ Au-{001}BiOCl produces high-energy active species to activate toluene and accelerate the cycle conversion of lattice oxygen and oxygen vacancy in MnO x .