Various degrees of palmitoylated konjac glucomannan (PKGM) are prepared by a heterogeneous method. Differential thermal analysis thermographs show PKGM having 0.51 degrees of substitution (DS) gave a new crystalline peak at higher temperature. With the increase of DS, the former crystalline state of konjac glucomannan will disappear; PKGM : 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 and oil in water systems. It is demonstrated that it is a kind of good water in oil emulsifier, with the DS ranged between 1.00 and 1.70, whereas DS < 0.50. It is a kind of good oil in water emulsifier and an interesting phenomenon appears in the water in oil system.