The selective decomposition of microcrystalline cellulose (MCC) by Fe-resin (a modified Dowex 50 by cation-exchange) solid catalyst in 5 wt % NaCl solution under hydrothermal conditions has been investigated. The conversion of MCC increases from 24.4% (without catalyst) to 90.9%, and the yield of glucose and levulinic acid (LA) increases from 0.6% and 1.1% (without catalyst) to 38.7% and 33.3%, respectively, under 200 degrees C for 5 h. The role that Fe-resin/NaCl played in the system is discussed in detail: NaCl could disrupt the hydrogen-bond matrix among cellulose fibers to change highly crystalline cellulose into an amorphous form; Lewis acids on the Fe-resin further boost the depolymerization of amorphous cellulose into water-soluble sugars (WSSs); Fe ions on Fe-resin progressively released into NaCl solution are beneficial to the conversion of WSSs to glucose and LA. A three-step degradation scheme reflecting the main pathways of MCC degradation in the reaction is proposed.