This research aimed to enhance the properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) biocomposites by incorporating hemp microcrystalline cellulose (MCC). Additionally, to improve interfacial adhesion between PHBV and MCC phases, a compatibilizer consisting of epoxidized natural rubber (ENR) grafted with microfibrillated cellulose (MFC) modified by vinyltrimethoxysilane (ENR-vinyl silanized MFC) was introduced. The addition of 5 wt% MCC increases the flexural modulus by approximately 65%. The use of ENR-vinyl silanized MFC as a compatibilizer demonstrated improved compatibility, as observed in scanning electron microscope (SEM) images. After 30 days of accelerated weathering (QUV) exposure, the flexural strength of the PHBV-based biocomposite with ENR-vinyl silanized MFC and MCC (vinyl silanized MFC biocomposite) was superior to that of the other samples. The remaining flexural strength can be sequentially categorized as follows: vinyl silanized MFC > MFC > non-MFC > PHBV. The T-g of PHBV-based biocomposites showed no significant change. Interestingly, the crystallinity of the vinyl silanized MFC biocomposite was the highest among all materials and demonstrated higher hydrophobicity. This makes the vinyl silanized MFC biocomposite a suitable material for construction, furniture, and both exterior and interior decoration.