For the synthesis of biocomposite materials for useful applications, it becomes necessary to modify the surface of natural fibers through chemical treatments. Morphology, structure and properties of natural fibers have an obvious effect on the mechanical properties of the biocomposite materials. It is thus necessary to know the morphology, thermal stability and crystalline behavior of original and modified fibers. In present paper, sunn hemp fibers (SHF) were chemically modified with ethyl acrylate and binary monomers (EA+MMA, EA+AA) through microwave radiations induced graft copolymerization. Various reaction parameters were optimized to get maximum grafting (91.8%). Morphology, thermal stability and crystalline behavior of original and modified fibers were investigated. Morphological and thermal studies showed that surface of sunn hemp fibers becomes rough and amorphous through graft copolymerization and thermal stability has been found to be increased. Microwave radiation induced grafting showed a diminutive effect on the crystalline behavior of the sunn hemp fibers as optimum time to get maximum grafting is very less (40 min) in comparison to conventional grafting. Synthesized graft copolymers were used as reinforcing material in preparation of polyhydroxybutyrate biocomposites. It has been observed that graft copolymers improved the interface between fiber and matrix and enhanced the mechanical strength of composites.