Spent lithium-ion batteries containing lots of strategic resources such as cobalt and lithium are considered as an attractive secondary resource. In this work, an environmentally compatible process based on vacuum pyrolysis, oxalate leaching and precipitation is applied to recover cobalt and lithium from spent lithium-ion batteries. Oxalate is introduced as leaching reagent meanwhile as precipitant which leaches and precipitates cobalt from LiCoO2 and CoO directly as CoC2O4·2H2O with 1.0M oxalate solution at 80°C and solid/liquid ratio of 50gL−1 for 120min. The reaction efficiency of more than 98% of LiCoO2 can be achieved and cobalt and lithium can also be separated efficiently during the hydrometallurgical process. The combined process is simple and adequate for the recovery of valuable metals from spent lithium-ion batteries.