The thermal and mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate, PHBV) composites filled with boron nitride (BN) particles with two different sizes and shapes were studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), thermal gravimetric analysis (TGA) and mechanical testing. The biocomposites were produced by melt extrusion of PHBV with untreated BN and surface-treated BN particles. Thermogravimetric analysis (TGA) showed that the thermal stability of the composites was higher than that of neat PHBV while the effect of the different shapes and sizes of the particles on the thermal stability was insignificant. DSC analysis showed that the crystallinity of the PHBV was not affected significantly by the change in filler concentration and the type of the BN nanoparticle but decreasing of the crystallinity of PHBV/BN composites was observed at higher loadings. BN particles treated with silane coupling agent yielded nanocomposites characterized by good mechanical performance. The results demonstrate that mechanical properties of the composites were found to increase more for the silanized flake type BN (OSFBN) compared to silanized hexagonal disk type BN (OSBN). The highest Young's modulus was obtained for the nanocomposite sample containing 1 wt.% OSFBN, for which increase of Young's modulus up to 19% was observed in comparison to the neat PHBV. The Halpin-Tsai and Hui-Shia models were used to evaluate the effect of reinforcement by BN particles on the elastic modulus of the composites. Micromechanical models for initial composite stiffness showed good correlation with experimental values.