Water-insoluble β - ( 1 - 3 ) – D - glucan isolated from the sclerotium of Poria cocos hardly exhibits biological activity. Therefore, it is advantageous to produce a value-added product from Poria cocos. We extracted the β - ( 1 - 3 ) – D - glucan from the sclerotium of Poria cocos and synthesized a carboxymethylated derivative, carboxymethyl-pachyman (CMP). The influences on the degrees of substitution ( DS ) of CMP, for example, volume ratio of ethanol to water, [NaOH]/[MCA] ratio, reaction temperature and reaction time have been examined, respectively. The most favorable conditions for pachyman carboxymethylation are obtained with a [NaOH]/[MCA] ratio of 1.5, at 45°C for 60 minutes with a reaction medium consisting of a ethanol/water 80:20 (v/v) mixture.