The influence of chain lengths on interfacial performances of carbon fiber/polyarylacetylene composites was studied. For this purpose, four coupling agents, methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane and dodecyltrimethoxysilane, were grafted onto fiber surface to obtain different chain lengths. The resulting carbon fiber surface was characterized by XPS and dynamic contact angle test. Interfacial adhesion in the resulting fiber reinforced polyarylacetylene resin composites was also evaluated by fracture morphology analysis and interfacial shear strength test. It was found that the interfacial adhesion in composites greatly increased with chain lengths on fiber surface. The improvement of interfacial adhesion was attributed to the interaction between the chain of coupling agents on fiber surface and that of polyarylacetylene resin at the interface.