Solar-light driven reduction of CO₂ to CH₄ is a complex process involving multiple electron and proton transfer processes with various intermediates. Therefore, achieving high CH₄ activity and selectivity remains a significant challenge. Covalent organic frameworks (COFs) represent an emerging class of photoactive semiconductors with molecular level structural tunability, modular band gaps, and high charge carrier generation and transport within the network. Here, we developed a new heterocyclic triazole ring containing COF, TFPB-TRZ through the condensation reaction between 1,3,5-Tris(4-formylphenyl)benzene (TFPB) and 3,5-Diamino-1,2,4-triazole (TRZ). The TFPB-TRZ COF with multiple heteroatoms shows suitable visible light absorption, high CO₂ uptake capability and proper band diagram for CO₂ photoreduction. Photocatalysis results reveal a maximum CO₂ to CH₄ conversion of 2.34 mmol g⁻¹ with a rate of 128 μmol h⁻¹ g⁻¹ and high selectivity (~99%) using 1-Benzyl-1,4-dihydronicotinamide (BNAH) and triethylamine (TEA) as sacrificial agents. Under similar reaction condition in the presence of direct sunlight, TFPB-TRZ COF displays a maximum CH₄ yield of 493 μmol g^-1 with a rate of 61.62 μmol g^-1 h^-1, suggesting the robustness and light-harvesting ability of the COF photocatalyst. Femtosecond transient absorption (TA) spectroscopy study shows fast decay of excited state absorption (ESA) in the COF compared to TFPB building unit due to efficient electron transfer to the catalytic site in the framework. The mechanistic insight of CO₂ reduction to CH₄ is studied by DFT-based theoretical calculation, which is further supported by in situ diffuse reflectance spectroscopic (DRIFT) study. The DFT results unveil that the lone pair of electrons on nitrogen heteroatoms present in the triazole ring of TRZ moiety help in the stabilization of CO intermediate during CO₂ to CH₄ conversion. Overall, this work demonstrates the use of a metal-free, recyclable COF-based photocatalytic system for solar energy storage by CO₂ reduction.