In order to develope an efficient way for the synthesis of highly pure 1,4-sorbitan solution from sorbitol, some experimental studies were performed. The reaction showed first order reaction with activation energy of 118.3 KJ/mol. Color of the product solutions changed to brown with reaction temperature and reaction time. The equilibrium contents of 1,4-sorbitan increased with decrease in reaction pressure, but the content of major impurity, sorbide, showed maximum about 550 torr vacuum with H3PO4 catalyst. The reasonable catalyst configuration was 0.26 wt% PTSA and 1 wt% H3PO2 and optimum reaction temperature and pressure range was 110～120℃ and 700～720 torr vacuum, respectively. At optimum reaction conditions, we could obtain white product solutions of highly pure 1,4-sorbitan with sorbide less than 10 wt%. This white product solution is advantageous for preparation of high quality span, anti-fogging agent.