The conjugated co-monomer, trimesic acid (TMA) was integrated into the triazine framework of polymeric carbon nitride (PCN), synthesized through chemical condensation of urea. The TMA-modified carbon nitride samples obtained were named as CNU-TMA and it was utilized for the photocatalytic reduction of carbon dioxide (CO2) under visible light illumination. The induction of such electron donor-acceptor co-monomer (TMA) dominates the intramolecular structure of PCN by acting as a nucleophilic substitution substrate to facilitate the electron density in the π-electron conjugated system of PCN and thus elevate its photocatalytic activity. Also, this process of copolymerization with TMA, not only cause a significant diversion in the specific area, band gap, chemical composition, and structure of PCN but also promote efficient charge transport from ground state (HOMO) to the excited state (LUMO) of the PCN. For comparison, CNU samples modified with other co-monomers were prepared by the same method and were named as CNU-FDA (2,5-Furandicarboxylic acid), CNU-PDA (2,6-pyridinedicarboxylic acid), CNU-PTA (Phthalic acid). Similarly, co-monomer TMA was incorporated in other PCN precursors such as dyandicyanamide (DCDA), thiourea (SCN) and ammonium thiocyanate (NH2SCN) and was named as CND-TMA13.0, CNT-TMA13.0, and CNA-TMA13.0, respectively. Besides, the average weight ratio between urea and TMA was well tuned and also CNU-TMA13.0 gain a fabulous 16 fold-enhanced photocatalytic performance than blank CNU.