The invention belongs to the technical field of chemical processes and in particular relates to a catalytic hydrogenation treatment process for a chloropivalic chloride rectification residual liquid.The process comprises the following steps: putting water and hydrolysis aids into a chloropivalic chloride rectification residual liquid, and performing hydrolysis, and the hydrolysis aids are one ortwo of manganese chloride tetrahydrate or nickel chloride hexahydrate; and after hydrolysis is completed, performing layering, collecting a crude product of chloropivalic acid at an upper layer, transferring the crude product of chloropivalic acid into a hydrogenation tower, performing a catalytic hydrogenation reaction so as to obtain a crude product of trimethylacetic acid, and performing distillation on the crude product of the trimethylacetic acid, so as to obtain a finished product of the trimethylacetic acid. The hydrolysis aids are manganese chloride tetrahydrate and nickel chloride hexahydrate. By adopting the process, the chloropivalic chloride rectification residual liquid is converted and prepared as high-purity trimethylacetic acid, so that the chloropivalic chloride rectification residual liquid is no longer treated as a dangerous waste, and resource utilization of wastes is sufficiently achieved; waste emission is greatly reduced, three wastes can be reduced, the environment protection burden of a company can be alleviated, meanwhile, the production cost of a product can be lowered, and great economic benefits can be made.