Cathode material Li[Ni1/3Co1/3Mn1/3]O2 for lithium-ion batteries with layered hexagonal structure was successfully synthesized in sol-gel way. The influences of calcination temperature (from 700° to 1000°C) on the structure and electrochemical behaviors of Li[Ni1/3Co1/3Mn1/3]O2 were extensively investigated. The results of XRD show that all samples are isostructural with α-NaFeO2 with a space group R-3m. XPS analysis shows that the oxidation states of Co and Mn were Co3+ and Mn4+ respectively, while Ni exists as Ni2+ and Ni3+. The charge-discharge experiments show that the sample calcined at 850°C delivers 194.8mAh/g in the first cycle at C/5 rate in 2.5-4.3V potential range.