Cross-linked polystyrene/glass fiber composites were fabricated using cross-linked polystyrene (CLPS) as matrix and E-glass fiber as the reinforcement. Surfaces of E-glass fibers were modified by vinyl triethoxysilane (VTES), vinyl trimethoxysilane (VTMS) and γ-methacryloylpropyl trimethoxysilane (MPS). The treated glass fibers were analyzed by fourier transform infrared spectroscopy (FTIR). Dynamic mechanical thermal analysis (DMTA) and thermo-gravimetric analysis (TGA) were employed to investigate the effect of glass fibers surface modification on viscoelastic behavior and thermal properties. The morphology of fracture surfaces of various composites was observed by scanning electron microscopy (SEM). The results revealed that these coupling agents were connected to the surfaces of the fibers by chemical bonding. Dynamic mechanical properties as well as thermal stability of the composites were improved considerablely, but to varying degrees depending on the fiber modification. The diversities of improvement of properties were attributed to the different interfacial adhesion between CLPS matrix and the glass fibers. Cross-linked polystyrene / glass fiber composites were fabricated using cross-linked polystyrene (CLPS) as matrix and E-glass fiber as the reinforcement. Surfaces of E-glass fibers were modified by vinyl triethoxysilane (VTES), vinyl trimethoxysilane The treated glass fibers were analyzed by fourier transform infrared spectroscopy (FTIR). Dynamic mechanical thermal analysis (DMTA) and thermo-gravimetric analysis (TGA) were employed to investigate the effect of glass fibers surface modification on The morphology of fracture surfaces of various composites was observed by scanning electron microscopy (SEM). The results revealed that these coupling agents were connected to the surfaces of the fibers by chemical bonding. Dynamic mechanical properties as well as thermal stability of the composites were improved considerably, but to varying degrees depending on the fiber modification. The di versities of improvement of properties were attributed to the different interfacial adhesion between CLPS matrix and the glass fibers.