Positive electrode material LiNi1/2Mn1/2O2 was synthesized via the carbonate co-precipitation method and the hydroxide precipitation route to study the effects of the precursor on its structural and electrochemical properties. The results of X-ray diffraction and Rietveld refinement show that the carbonate precursor of Ni2+ and Mn2+ exhibits one phase at a pH of 8.5, while the hydroxide deposit separates into Ni(OH)2 and Mn(OH)2 phases under the same experimental conditions. LiNi1/2Mn1/2O2 material prepared from the hydroxide precursor shows 8.9% Li/Ni exchange and a large capacity loss of 11.3% in the first 10 cycles. By contrast, more uniform distribution of transition metal ions and stable Mn2+ in the carbonate precursor contribute to only 7.8% Li/Ni disorder in the obtained LiNi1/2Mn1/2O2, which delivers a reversible capacity of about 182 mAh g−1 at a current rate of 14 mA g−1 between 2.5 and 4.8 V.