A facile method was developed to fabricate porous tube-like ZnS by sulfurizing rod-like ZIF-L with thioacetamide (TAA) at different durations and the formation mechanism of the porous tube-like ZnS was discussed in detail. The series of sulfide products (ZS-X) were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), solid-state nuclear magnetic resonance spectroscopy (SSNMR), transmission electron microscopy (TEM), UV–visible diffuse-reflectance spectroscopy (UV–vis DRS). The photocatalytic performances of ZS-X toward Cr(VI) reduction and organic pollutant degradation were explored. It was discovered that ZS-3 (porous tube-like ZnS) exhibited excellent activities under UV light and displayed good reusability and stability after several experimental cycles. In addition, Cr(VI) reduction and organic pollutant degradation were investigated under different pH values and existence of different foreign ions. The photocatalytic activities of ZS-3 were tested toward the matrix of Cr(VI) and reactive red X–3B. The mechanism was proposed and verified by both electrochemical analysis and electron spin resonance (ESR) measurement.