Graphitic carbon nitride (g-C₃N₄) is paying attention lately owing to its interesting characteristics and substantial application in improving environmental and energy concerns. Nevertheless, the photocatalytic activity of g-C₃N₄ is constrained by the inertness of the surface and particle aggregation during photocatalytic activity. Herein, we report the preparation of g-C₃N₄ with honeycomb-like morphology (HC-C₃N₄) via thermal condensation of prepared SiO₂ templates and dicyandiamide. The etching out of the SiO₂ templates by NH₄HF₂ created hollow or macropores in the C₃N₄ matrix resulting in its structural changes. Similar, to the bulk C₃N₄, the HC-C₃N₄ exhibited higher photocatalytic CO₂ reduction in hydrocarbons. This improved photocatalytic achievement is associated with higher specific surface area, excellent visible light absorption capability, higher electron donor density, easy mass diffusion of materials for surface reaction, and effective segregation of photogenerated charge carriers. Furthermore, the HC-C₃N₄ honeycomb structure was deposited with Ni(OH)₂ clusters which showed remarkable CO₂ reduction activity of 1.48 μmolh⁻¹ g⁻¹ of CH₄ and 0.73 μmolh⁻¹ g⁻¹ of CH₃OH generation which is 3.5 and 4.3 times higher CO₂ reduction activity compared with bulk C₃N₄ clustered with Ni(OH)₂ particles. This comprehensive study demonstrated that HC-C₃N₄ nanostructured polymeric semiconductor is envisaged to have great potential in the application of a variety of fields such as photocatalysis, sensor technology, and nanotechnology.