The invention discloses a process for preparing tetrahydrate manganese chloride by leaching out rhodochrosite with waste acid. The process comprises the following steps of: adding waste hydrochloric acid to rhodochrosite step by step for leaching, meanwhile, adding pyrolusite or psilomelane which is used as an oxidant; filtering the generated mixed solution, and leaching the filter residue with acid once again; adding metal manganese powder to filter liquor for precipitating, filtering and abandoning slag; adding oxalic acid in the filter liquor for settling, filtering; adding manganese sulfate powder to the filter liquor for precipitating, and filtering; quantitatively adding BaCl2 to the filter liquor, standing still and filtering to remove excessive SO4 <2->; and finally, carrying out concentrating crystallization and centrifugal separation on the filter liquor to obtain a tetrahydrate manganese chloride product. Compared with the prior art, the process has the advantages of simple process flow, convenience of operation, less investment, high efficiency and easy utilization of industrialization. In the invention, low-concentration waste acid is used for leaching the rhodochrosite to produce tetrahydrate manganese chloride, which not only solves the treatment problem of waste acid, but also efficiently utilizes a large quantity of low-grade rhodochrosite resources and realizes the sustainable utilization of resources.