In the present study, cathode materials (C/LiCoO2) of spent lithium-ion batteries (LIBs) and waste polyvinyl chloride (PVC) were co-processed via an innovative mechanochemical method, i.e. LiCoO2/PVC/Fe was co-grinded followed by water-leaching. This procedure generated recoverable LiCl from Li by the dechlorination of PVC and also generated magnetic CoFe4O6 from Co. The effects of different additives (e.g. alkali metals, non-metal oxides, and zero-valent metals) on (i) the conversion rates of Li and Co and (ii) the dechlorination rate of PVC were investigated, and the reaction mechanisms were explored. It was found that the chlorine atoms in PVC were mechanochemically transformed into chloride ions that bound to the Li in LiCoO2 to form LiCl. This resulted in reorganization of the Co and Fe crystals to form the magnetic material CoFe4O6. This study provides a more environmentally-friendly, economical, and straightforward approach for the recycling of spent LIBs and waste PVC compared to traditional processes.