The present paper proposes a novel zero-energy solar application system combining the thermal catalytic technology with Trombe wall (TC-Trombe wall), which could realize indoor air purification and space heating simultaneously fully driven by solar energy. A full-day experiment was conducted to study the air heating performance and formaldehyde degradation performance of TC-Trombe wall. Results showed that the daily air heating efficiency was 41.3%. In our experiments, the generated total volume of fresh air and total formaldehyde degradation amount by TC-Trombe wall were 249.2 m(3)/(m(2) day) and 208.4 mg/(m(2) day), respectively. In addition, a photothermocatalytic synergetic effect exists in the solar light driven thermocatalytic oxidation process over MnOx-CeO2 catalysts. A dynamic numerical model was developed to predict system thermal properties. Based on the simulation results, the effects of the solar radiation intensity, ambient temperature and air layer thickness on the system thermal efficiency were discussed. Furthermore, the energy saving performance of TC-Trombe wall was evaluated in heating seasons in Hefei based the established system thermal model. Results showed that the total saving energy of up to 97.4 kW h/m(2) could be obtained. The saving energy for space heating and formaldehyde degradation were 64.3 kW h/m(2) and 33.1 kW h/m(2), respectively.