The photocatalyst-enzyme hybrid systems (PEHSs) provided a promising method for environmental remediation by simultaneously harnessing the power of solar-energy conversion and biocatalysis. However, the use of PEHSs for environmental remediation was restricted by a complicated synthesis and assembly process. This work explored a simple one-pot biomineralization approach to fabricate PEHS. It was found that the cytochrome enzyme could be directly self-assembled onto the biosynthesized CdS during biomineralization by Shewanella oneidensis MR-1. More strikingly, those attached cytochrome enzymes could efficiently receive the photoelectrons from the CdS and serve as the photoreduction center which formed a typical PEHS. Impressively, this bio-CdS-cytochrome PEHS exhibited an extremely high photocatalytic decolorization rate of 69.4 mg/g/min, which was the highest record ever reported for procion red H-E3B. This work provided a simple and facile approach for PEHSs fabrication, which would be promising for practical application in environmental remediation.