The synthesis of highly crystalline mesoporous materials is key to realizing high-performance chemical and biological sensors and optoelectronics. However, minimizing surface oxidation and enhancing the domain size without affecting the porous nanoarchitecture are daunting challenges. Herein, we report a hybrid technique that combines bottom-up electrochemical growth with top-down plasma treatment to produce mesoporous semiconductors with large crystalline domain sizes and excellent surface passivation. By passivating unsaturated bonds without incorporating any chemical or physical layers, these films show better stability and enhancement in the optoelectronic properties of mesoporous copper telluride (CuTe) with different pore diameters. These results provide exciting opportunities for the development of long-term, stable, and high-performance mesoporous semiconductor materials for future technologies.