© The Author(s) 2016. The main objective of this work was to explore for the first time the potential of the co-grinding process using a high-energy vibrated ball mill to prepare poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/wheat straw fibers biocomposites. Grinding conditions of virgin PHBV pellets were examined by focusing on the evolution of particle size, morphology, crystallinity, and molecular weight. Temperature and grinding duration were demonstrated to be the key parameters affecting PHBV milling. In a second step, mechanical properties of biocomposites prepared by cryo-co-grinding were discussed in relation to the processing conditions and the resulting structure of materials. Comparing to virgin PHBV, the reinforcing effect of wheat straw fibers was very poor, regardless of the good dispersion of fibers within the polymer matrix induced by co-grinding. The increased brittleness and decreased toughness of biocomposites were attributed to (a) a poor interfacial compatibility between wheat straw fibers and PHBV and (b) the degradation of PHBV during processing, as revealed by the decrease in molecular weight.