Synthesis of Li2MnSiO4 was attempted by the conventional solid-state reaction method, and the phase formation behavior according to the change of the calcination condition was investigated. When the mixture of the three source materials, Li2O, MnO and SiO2 powders, were used for calcination in air, it was difficult to develop the Li2MnSiO4 phase because the oxidation number of Mn2+ could not be maintained. Therefore, two-step calcination was applied: Li2SiO3 was made from Li2O and SiO2 at the first step, and Li2MnSiO4 was synthesized from Li2SiO3 and MnO at the second step. It was easy to make Li2SiO3 from Li2O and SiO2. Li2MnSiO4 single phase was developed by the calcination at 900℃ for 24 hr in Ar atmosphere as the oxidation of Mn2+ was prevented. However, the Li2MnSiO4 was γ -Li2MnSiO4, one of the polymorph of Li2MnSiO4, which could not be used as the cathode materials in Li-ion batteries. By applying the additional low temperature annealing at 400℃, the single phase β -Li2MnSiO4 powder was synthesized successfully through the phase transition from γ to β phase.