Spherical LiNi0.75Co0.25O2 compounds were synthesized by sintering spherical Ni0.75Co0.25(OH)2 and LiOH·H2O precursors at various temperatures in an oxygen atmosphere. A pure phase LiNi0.75Co0.25O2 could be identified. SEM observation showed that the LiNi0.75Co0.25O2 particles are spherical in shape and are composed of many small crystals. Magnetic susceptibility measurements reveal that the spherical LiNi0.75Co0.25O2 compounds have a more ordered layered structure than that of non-spherical LiNi0.75Co0.25O2. The spherical LiNi0.75Co0.25O2 cathodes demonstrated a stable electrochemical performance in lithium-ion cells with a high reversible capacity of 167mAh/g and good cyclability.