Degradation of cellulose to reducing sugar is the key step for the conversion of cellulose to valuable chemicals. Cellulose was degraded by WCl₆ in 1-butyl-3-methyl imidazole chloride at 80 °C and lower. 83% and 85.5% yield of total reducing sugar was gotten at 70 and 80 °C, respectively. Compared with inorganic acid, heteropoly acid, acidic ionic liquid and other metal chlorides, WCl₆ has shown better catalytic performance for degradation of cellulose to reducing sugar. The effect of reaction temperature, reaction time, WCl₆ amount and cellulose concentration were investigated. Degradation of cellulose by WCl₆ in 1-butyl-3-methyl imidazole chloride is a zero reaction. WCl₆ also showed excellent catalytic performance for the degradation of nature cellulose and lignocellulose. Catalyst can be reused at least 5 times without decrease of reducing sugar yield. The mechanism of degradation of WCl₆ was also suggested.