Environmental contamination by hexavalent chromium (Cr(VI)) and antibiotic drug residues pose significant challenges to public health and ecosystems. This study investigates the application of CoTiO3/BiVO4@MIL-Fe(53) (CT/BV@Fe-MOF) for the reduction of Cr(VI) and degradation of tetracycline (TCL) under visible light. After grafting an iron-based metal–organic framework MIL-Fe(53) on a modified CoTiO3/BiVO4 composite, the photogenerated electrons could easily be transferred from CoTiO3 to BiVO4/Fe-MOF species via interfacial charge transfer. UV–vis diffuse reflectance spectroscopy showed that charge carriers were formed in response to visible light absorption. The effect of different operating parameters, including catalyst load, pH, initial Cr(VI), and TCL concentration, was systematically evaluated during the photocatalytic process. The CT/BV@Fe-MOF composite exhibited 98.7% reduction efficiency in Cr(VI) (50 ppm) and 97.5% degradation efficiency towards TCL (30 ppm) within 90 min, resulting in a greater efficiency than the pristine CoTiO3, BiVO4, and Fe-MOF materials. The CT/BV@Fe-MOF composite displayed excellent stability over six cycles, highlighting its potential for practical applications. In addition, the plausible degradation pathway of TCL was evaluated using LC-ESI/MS analysis, while the TEST program was utilized to investigate the toxicity of the products generated during the degradation process.