In this paper, a novel double-skin ventilated purified window integrated with solar photo-thermal conversion/ synergistic-catalytic blinds that realized the functions of space heating, air purification and shading was proposed. Firstly, experimental tests on the hybrid system with solar photo-thermal conversion/synergistic-catalytic blinds were conducted under different blind turning angles. Secondly, the heat and mass transfer model of proposed system was developed and verified experimentally. Thirdly, the thermal and formaldehyde degradation performance applied in five cities under various blind turning angles were investigated to acquire the annual optimal operation strategy on blind angle. Main results were: (1) The photo-thermal composite catalyst behaved better formaldehyde removal performance compared with single thermal catalytic material. (2) The RMSD values of air outlet temperature, air thermal efficiency, formaldehyde outlet concentration, and CADR calculated by the established model were 1.8%, 7.1%, 2.1% and 8.5%, respectively. (3) Applying the annual optimal operation strategy on blind angle in Beijing, Nanjing, Hefei, Guangzhou and Xining, the annual total reduced heating load was 375.12, 276.42, 202.22, 124.49 and 947.61 MJ/m2. The annual total reduced cooling load was 257.78, 193.10, 355.87, 345.11 and 0 MJ/m2. The annual total generated clean air was 11393.11, 9868.48, 8367.68, 7151.36 and 18135.83 m3/m2.