In this paper, green biocomposites based on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) and Miscanthus giganteus fibers (MIS) were prepared in the presence of dicumyl peroxide (DCP) via reactive extrusion. The objective of this study was to optimize the interfacial adhesion between the reinforcement and the matrix, improving the mechanical properties of the final material. To this aim, two fibers mass fractions (5 and 20 wt %) and two different fiber sizes obtained by two opening mesh sieves (1 mm and 45 m) were investigated. The impregnation of fibers with DCP before processing was carried out in order to promote the PHBHV grafting onto MIS fibers during the process, favoring, in this way, the interfacial adhesion between fibers and matrix, instead of the crosslinking of the matrix. All composites were realized by extrusion and injection molding processing and then characterized by tensile tests, FTIR-ATR, SEM, DSC and XRD. According to the improved adhesion of fibers to matrix due to DCP, we carried out an implementation of models involving that can predict the effective mechanical properties of the biocomposites. Three phases were taken into account here: fibers, gel (crosslinked matrix), and matrix fractions. Due to the complexity of the system (matrix-crosslinked matrix-fibers) and to the lack of knowledge about all the phenomena occurring during the reactive extrusion, a mathematical approach was considered in order to obtain information about the modulus of the crosslinked matrix and its fraction in the composites. This study aims to estimate these last values, and to clarify the effect caused by the presence of vegetal fibers in a composite in which different reactions are promoted by DCP.