The current clean synthesis processes and the main research direction on synthesis of hexameth- ylene-1,6-diisocyanate(HDI) are reviewed. The advantages and disadvantages of the synthesis processes are compared. The method of methoxycarbonylation of 1,6-hexanediamine with dimethylcarbonate to synthesize dimethylhexane-1,6-dicarbamate is presented,then the catalytic decomposition of dimethylhex- ane-1,6-dicarbamate to hexamethylene-1,6-diisocyanate is introduced emphatically. The prospect of clean synthesis of hexamethylene-1,6-diisocyanate is proposed.