Li0.74MoO2, Li0.85MoO2, and Li1.00MoO2 have been synthesized using a carbothermal reduction approach. X-ray diffraction indicates that the phases all possess a hexagonal layered structure related to alpha-NaFeO2. Preliminary electrochemical evaluation suggests that specific capacities close to theoretical may be attained for the Li0.85MoO2 and Li1.00MoO2 compounds. High-resolution measurements reveal the presence of multiple phase transitions during the lithium insertion process with formation of an ordered composition close to x=0.5 in LixMoO2. The carbothermal approach appears to offer an economical method for the commercial synthesis of various single-phase compounds in the Li-Mo-O phase diagram. (C) 2003 The Electrochemical Society.