The design and fabrication of functional hydrogel materials for environmental catalysis is a frontier topic both in fields of material science and catalysis. In this study, a new cellulosic hydrogel anchoring 1,1,3,3-tetramethyl guanidinium-based ionic liquids moiety (CHI) was firstly prepared by simply adding bicyclic anhydrides into newly developed 1,1,3,3-tetramethyl guanidine/DMSO/CO2 solvent system for cellulose. The presence and amount of bicyclic anhydrides as a cross linker was proved to be an important factor for the hydrogel formation. And then, Pd nanoparticles (NPs)@CHI composites were fabricated by the reduction of the absorbed Pd(II) ions on CHI using NaBH4 as reducing agent. The samples were characterized by techniques of H-1 NMR, C-13 NMR, FTIR, SEM, TEM, EDX, XPS, XRD and ICP-OES analysis. It was identified that the CHI presented good immobilization capacity of Pd NPs, and the achieved Pd NPs@CHI composite had high catalytic activity and excellent reusability for the reduction of 4-nitrophenol in water. The activation parameters of the reduction reaction of 4-nitrophenol catalyzed by Pd NPs@CHI using NaBH4 were calculated as Ea = 10.8 kJ mol(-1), Delta H-# = 8.1 kJ mol(-1) and Delta S-# = -234.8 J mol(-1) K-1.