Various degrees of paimitoylated konjac glucomannan (PKGM) are prepared by heterogeneous method. Differential thermal analysis (DTA) thermographs show PKGM having certain degree of substitution (DS) gave a new crystalline peak at higher temperature. And PKGM having higher DS only shows the new crystalline state. Furthermore, the effect of the DS of PKGM on its emulsifying ability has been investigated in the water in oil (w/o) and oil in water (o/w) systems. It is demonstrated that it is a kind of good w/o emulsifier with the DS ranged between 1.00 and 1.70; Whereas for DS<0.50, It is a kind of good o/w emulsifier and an interesting phenomenon appears in o/w system. And the half-time of emulsion turbidity is more than 1.5 h with PKGM having 2.72 of DS used as the emulsifier.