A novel strategy for the synthesis of main-chain Azo polymers directly from bisnitroaromatic compounds by the photocatalytic process has been achieved under mild conditions. This approach avoids the tedious synthesis of Azo monomers and proceeds with a high monomer conversion (similar to 100%) and excellent selectivity (similar to 100%) but without generating a significant amount of inorganic wastes and impurities (Cu2+ or azoxy groups) existing in main-chain Azo polymers compared to previous methods. The polymerization was monitored by UV-vis, FT-IR, and MALDI-TOF-MS, indicating that the reaction process proceeded with formation of the azoxy repeating units from the corresponding bisnitroaromatic monomers and the reduction of corresponding azoxy repeating units to the azo repeating units. Furthermore, the recyclable heterogeneous photocatalysts represent an attractive green process for production of main-chain Azo polymers.