The enzymatic hydrolysis of the native and the pretreated palm pressed fiber (PPF) was deeply investigated by using the enzyme cocktail ACCELLERASE 1500. Together with the spent PPF from the first hydrolysis and the further doubly-treated PPF, the proportions of three main components were determined and analyzed based on a triangle figure. The proportion (cellulose/hemicelluloses/lignin) in the spent PPF was equal to 44:23:33 and the surface morphology of the spent PPF looks very similar to the native PPF surface showing poor hydrolysis efficiency. After further double treatment, the proportion was changed evidently from the original 44:23:33 to 54:21:25 and the surface structure was significantly disrupted showing a potential to be hydrolyzed completely. Additionally, all samples were characterized by Fourier transform infrared spectroscopy and X-ray diffractogram through considerations of alkaline solution treatment, so as to understand better the nature of biomass hydrolysis, from the aspect of three biomass components.