Cobalt ferrite nanoparticles are a soft magnetic material have been extensively used in many electronic and magnetic applications. In this study, Co0.8Fe2.2O4 nanoparticles with particle size of about 23.5 nm were directly synthesized by sol-gel auto-combustion and calcination methods using spent Li-ion batteries as raw materials. The overall process involves four steps: formation of homogeneous sols; formation of dried gels; combustion of the dried gels; and calcination of the dried gels after combustion at 1173 K for 2 h. The DTA-TG and IR were used to study the auto-combustion and thermal decomposition of the precursor, the morphology and structure of cobalt ferrite nanoparticles were characterized by XRD and TEM techniques. Moreover, the precise metal ion stoichiometry of cobalt ferrite nanoparticles was analyzed by ICP. The results revealed that the auto-combustion process was considered as a heat-induced exothermic oxidation-reduction reaction between nitrate ions and carboxyl group. The XRD patterns of calcination the dried gels after combustion confirmed the single phase spinel structure for the synthesized materials. The crystallite size was calculated from the most intense peak (3 1 1) using the Scherrer equation. The TEM photograph also shown that cobalt ferrite nanoparticles were well-dispersed and with little aggregation.