The influence of various alkali and alkaline earth metal chlorides (LiCl, NaCl, KCl, MgCl₂, and CaCl₂) on primary and secondary char formation from cellulose was studied at 400°C. Secondary char was formed through carbonization of the volatile products. All chlorides increased the primary char yield while decreasing the secondary char formation, and this situation was promoted in the order of alkaline earth Mg, Ca, alkali Li > alkali Na, K. Levoglucosan yield also decreased along with the secondary char yield. These results indicate that the reduced formation of volatile levoglucosan was related to the decreasing yield of secondary char. A model experiment at 250°C revealed that these chlorides, especially the two alkaline earth metals, had catalytic action on the polymerization of levoglucosan, which serves to reduce the formation of volatile levoglucosan.