A rotating packed bed (RPB) reactor has substantially potential for the process intensification of heterogeneous catalytic reactions. However, the scarce knowledge of the liquid–solid mass transfer in the RPB reactor is a barrier for its design and scale-up. In this work, the liquid–solid mass transfer in a RPB reactor installed with structured foam packing was experimentally studied using copper dissolution by potassium dichromate. Effects of rotational speed, liquid and gas volumetric flow rate on the liquid–solid mass transfer coefficient (kLS) have been investigated. The correlation for predicting kLS was proposed, and the deviation between the experimental and predicted values was within ± 12%. The liquid–solid volumetric mass transfer coefficient (kLSaLS) ranged from 0.04–0.14 1−1, which was approximately 5 times larger than that in the packed bed reactor. This work lays the foundation for modeling of the RPB reactor packed with structured foam packing for heterogeneous catalytic reaction.