Semiconductor materials with pore structure have excellent physicochemical properties for photocatalytic reactions. Here, the one-step vulcanization of Cd-based MOF solid rods was successfully developed to synthesize two kinds of CdS rods with pore structure: hollow rods (HRs) and mesoporous rods (MRs). Among the three catalysts, the CdS HRs showed the highest photocatalytic efficiency, which could remove about 96.0% of RhB in 30 min under visible light irradiation. The enhanced photocatalytic activity of CdS HRs benefits from its novel hollow structure, which enhances the visible light absorption capability and the separation efficiency of photogenerated electron–hole pairs. The successful synthesis of CdS HRs has guiding significance for the design and synthesis of other hollow structures with high photocatalytic activity.