Although several complexes of thiamine and inorganic compounds had been reported in several literatures, the thiamine-sodium compounds have not been identified as yet. While conducting studies for the purpose of synthesizing thiamine-calcium-phosphorus compounds, we found a method for synthesizing thiamine-sodium precipitate in the trial processes. Based on the findings of elemental analysis, FT-IR analysis, and HPLC and TLC analysis, the formation of the thiamine-sodium complex was firmly confirmed.