Heterostructured composites with an excellent photocatalytic activity have attracted increasing attention because of their great application in environmental remediation. Herein, a MIL-101(Fe)/g-C3N4 heterojunction was synthesized via in-situ growth of MIL-101(Fe) onto g-C3N4 surface. The heterojunctions were applied as a bifunctional photocatalyst for simultaneous reduction of Cr(VI) and degradation of bisphenol-A (BPA) under visible light and exhibited an obvious enhancement in photocatalytic performance compared with MIL-101(Fe) or g-C3N4. The improved activity could be attributed to the enhanced light absorption and efficient charge carrier separation by forming a direct Z-scheme heterojunction with appropriate band alignment between MIL-101(Fe) and g-C3N4. The radical trapping and electron spin resonance showed that photo-generated electrons are responsible for the reduction of Cr(VI) and BPA degradation, following an oxygen-induced pathway. This work provides new insight into the construction of metal-free semiconductor/MOFs heterojunctions as a bifunctional visible-light-driven photocatalyst for efficient and simultaneous treatment of multiple toxic pollutants in water.