Miscanthus biocarbon (MB), a renewable resource-based, carbon-rich material, was melt-processed with poly (3-hydroxybutyrate- co -3-hydroxyvalerate) (PHBV) to produce sustainable biocomposites. The addition of the biocarbon improved the Young’s modulus of PHBV from 3.6 to 5.2 GPa at 30 wt % filler loading. An increase in flexural modulus, up to 48%, was also observed. On the other hand, the strength, elongation-at-break and impact strength decreased. Morphological study of the impact-fractured surfaces showed weak interaction at the interface and the existence of voids and agglomerates, especially with high filler contents. The thermal stability of the PHBV/MB composites was slightly reduced compared with the neat PHBV. The biocarbon particles were not found to have a nucleating effect on the polymer. The degradation of PHBV and the formation of unstable imperfect crystals were revealed by differential scanning calorimetry (DSC) analysis. Higher filler contents resulted in reduced crystallinity, indicating more pronounced effect on polymer chain mobility restriction. With the addition of 30 wt % biocarbon, the heat deflection temperature (HDT) became 13 degrees higher and the coefficient of linear thermal expansion (CLTE) decreased from 100.6 to 75.6 μm/(m·°C), desired improvement for practical applications.