Large-scale and high-quality Cu2O microcrystalline films with high photoactivity are synthesized using a novel and low-cost method. The enhanced photoactivity is achieved through the formation of Cu2O microcrystalline films having well-defined crystal facets and porous structure. Cu2O microcrystalline films are fabricated by decomposing previously synthesized Cu(OH)2 nanowires on a Cu foil under a vacuum. Subsequent crystal growth during the annealing process is driven by outward diffusion of Cu ions and oxidation. Crystal growth induces coalescence of the nanowires and results in the formation of Cu2O microcrystals enclosed by four {111} facets. Photoelectrochemical evaluation of the annealed samples performed under chopped simulated AM 1.5G illumination reveals that the sample annealed at 500 °C for 2 h exhibited the highest photocurrent of 4.07 mA/cm(2) at 0 V/RHE. This large photocurrent is ascribed to a high carrier density (~1.36 × 10(18) cm(-3)) and a low carrier transfer resistance in electrolyte, as evidenced by electrochemical impedance spectroscopy. The obtained low-cost Cu2O microcrystalline film (2 h) may serve as an excellent solar absorber and carrier provider for use in photovoltaics and artificial photosynthesis.