Metal-assisted chemical etching (MaCE) has been widely employed for the fabrication of regular silicon (Si) nanowire arrays. These features were originated from the directional etching of Si preferentially along <100> orientations through the catalytic assistance of metals, which could be gold, silver, platinum or palladium. In this study, the dramatic modulation of etching profiles toward pyramidal architectures was undertaken by utilizing copper as catalysts through a facile one-step etching process, which paved the exceptional way on the texturization of Si for advanced photovoltaic applications. Detailed examinations of morphological evolutions, etching kinetics and formation mechanism were performed, validating the distinct etching model on Si contributed from cycling reactions of copper deposition and dissolution under a quasi-stable balance. In addition, impacts of surface texturization on the photovoltaic performance of organic/inorganic hybrid solar cells were revealed through the spatial characterizations of voltage fluctuations upon light mapping analysis. It was found that the pyramidal textures made by copper-induced cycling reactions exhibited the sound antireflection characteristics, and further achieved the leading conversion efficiency of 10.7%, approximately 1.8 times and beyond 1.2 times greater than that of untexturized and nanowire-based solar cells, respectively.