Materials that are both biodegradable and bio-sourced are becoming serious candidates for substituting traditional petro-sourced plastics that accumulate in natural systems. New biocomposites have been produced by melt extrusion, using bacterial polyester (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)) as a matrix and cellulose particles as fillers. In this study, gas-phase esterified cellulose particles, with palmitoyl chloride, were used to improve filler-matrix compatibility and reduce moisture sensitivity. Structural analysis demonstrated that intrinsic properties of the polymer matrix (crystallinity, and molecular weight) were not more significantly affected by the incorporation of cellulose, either virgin or grafted. Only a little decrease in matrix thermal stability was noticed, this being limited by cellulose grafting. Gas-phase esterification of cellulose improved the filler’s dispersion state and filler/matrix interfacial adhesion, as shown by SEM cross-section observations, and limiting the degradation of tensile properties (stress and strain at break). Water vapor permeability, moisture, and liquid water uptake of biocomposites were increased compared to the neat matrix. The increase in thermodynamic parameters was limited in the case of grafted cellulose, principally ascribed to their increased hydrophobicity. However, no significant effect of grafting was noticed regarding diffusion parameters.