Activity of a catalyst can be improved either by increasing the surface area, intrinsic activity (photon absorption and redox potential) or by limiting the electron−hole recombination. The surface area can be increased by reducing the size, while band gap engineering can reduce the band gap, thereby enhancing the light-driven functionality of a semiconductor. The position of the energy level decides the intrinsic activity and also the electron−hole recombination probability. Here, we have reported the role of various parameters by the engineering of the band structures of a three-dimensional (3D)−two-dimensional (2D) ZnO hybrid consisting of porous 3D and sheet-like 2D structures through nitrogen− carbon codoping. The hybrid 3D−2D structures are obtained through a simple and cost-effective hybrid approach (coprecipitation and open-air combustion). Co-doping of nitrogen and carbon occupies the lattice oxygen and interstitial sites, respectively, and generates mid-gap states at 2.2 and 2.7 eV for maximal co-doped ZnO. Interestingly, the as-mentioned hybrid displays the highest degradation of rhodamine B under visible light due to its highest photon absorption capacity and demonstrates its visible light-driven functionality. Moreover, a unique approach for the reusability test has been adopted, which demonstrates the reusability of the catalyst without deterioration in activity at least for six cycles. Overall, we believe that the present study will motivate the researchers to further explore the area of midgap state engineering to achieve visible light-driven activity of wide band gap semiconductors.