In this work, an effective and environmentally friendly process for the recovery of cobalt (Co) and lithium (Li) from spent lithium-ion batteries (LIBs) and simultaneously detoxification of polyvinyl chloride (PVC) in subcritical water was developed. Lithium cobalt oxide (LiCoO2) power from spent LIBs and PVC were co-treated by subcritical water oxidation, in which PVC served as a hydrochloric acid source to promote metal leaching. The dechlorination of PVC and metal leaching was achieved simultaneously under subcritical water oxidation. More than 95% Co and nearly 98% Li were recovered under the optimum conditions: temperature 350 degrees C, PVC/LiCoO2 ratio 3:1, time 30 min, and a solid/liquid ratio 16:1 (g/L), respectively. Moreover, PVC was completely dechlorinated at temperatures above 350 degrees C without any release of toxic chlorinated organic compounds. Assessment on economical and environmental impacts revealed that the PVC and LiCoO2 subcritical co-treatment process had significant technical, economic and environmental benefits over the traditional hydrometallurgy and pyrometallurgy processes. This innovative co-treatment process is efficient, environmentally friendly and adequate for Co and Li recovery from spent LIBs and simultaneous dechlorination of PVC in subcritical water. (C) 2016 Elsevier B.V. All rights reserved.