This study develops a urea-based homogeneous precipitation method to synthesize spherical carbonate precursors (Ni0.25Mn0.75CO3) for the Li-rich layered cathode material Li(Ni0.2Li0.2Mn0.6)O2. The structure and morphology of the precursor particles were tailored by controlling of urea concentration, reaction temperature and time. Combined with XRD, SEM, and particle size analysis, the optimized conditions for synthesizing desired stoichiometric Ni0.25Mn0.75CO3 were obtained. We also investigated the processes of nucleation and growth of precursors. The obtained spherical Li(Ni0.2Li0.2Mn0.6)O2 delivers discharge capacity of 237 mAh g−1 at the initial cycle and 253 mAh g−1 after 50 cycles.