Well-ordered high-temperature LiCoO2 (HT-LiCoO2) is synthesized by mechanical alloying (MA) of LiOH·H2O and Co(OH)2 powders and subsequent firing. Its electrochemical properties are investigated. The maximum discharge capacity of a sample mechanically alloyed and fired at 600°C for 2h is 152mAhg−1 at the C/40 rate, which is comparable to that obtained from a sample made by conventional solid state reactions. The cycleability is inferior, however, due to a relatively low crystallinity. When the firing temperature is increased to 850°C, the first discharge capacity of 142mAhg−1 at the C/5 rate is increased by more than 10%, and retains 93% of its maximum value after 30 cycles. These cycling properties are about the same, or slightly higher, than those synthesized by firing a sample mixture of the same starting materials at 600°C for 8h and then at 850°C for 24h. Consequently, given the lower firing temperature and/or reduced reaction time, MA could prove a promising synthetic process for cathode materials used in rechargeable lithium batteries.