It is of great significance to exploit environmentally friendly, efficient and economical catalysts for dealing with wastewater and other aquatic environments. In this study, a series of P-doped Cu/Cu2O/C heterostructures were obtained by controlled calcination of corncobs supported Cu-MOF in different temperature. Comprehensive structural characterizations indicate the polyhedron morphology and high porosity of [email protected] The composites were further explored as an efficient catalyst for catalytic reduction of 4-nitrophenol (4-NP). Remarkably, [email protected] could efficiently catalyze the reduction of 4-NP, and the reduction could be finished within 90 s with a 4-aminophenol (4-AP) selectivity of >99%, demonstrating the excellent performance of Cu-based catalysts for 4-NP reduction. The application scope could be further expanded to the catalytic reduction of ofloxacin and a conversion of 95.7% could be achieved within 10 min. Reproducibility studies and characterizations comprehensively demonstrate the promising potential of [email protected] acting as efficient catalyst for the reductive removal of environmental pollutants. This work provides a facile strategy for the fabrication of highly active catalysts for high-performance environmental purification, and the employment of renewable bioresources and functional MOFs represents a promising strategy for design and synthesis of highly active catalysts towards various advanced applications.