The green nanocomposites of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with various cellulose nanocrystals (CNCs) contents were prepared by solution casting method. The effects of CNCs on the crystallization behavior, spherulitic morphology, crystal structure and hydrophilic property of PHBV were studied by differential scanning calorimeter (DSC), polarized optical microscope (POM), wide-angle X-ray diffraction (WAXD) and static water contact angle measurement. It is found that the CNCs act as an effective nucleation agent for crystallization of PHBV, inducing an increase in the melt crystallization temperature of the nanocomposites. A study of the non-isothermal crystallization kinetics further illustrated that overall crystallization rate of PHBV in the nanocomposites was faster than that of neat PHBV, but exhibited a decrease in the crystallinity and the spherulite size of PHBV. Furthermore, the contact angle decreased from 60.1° for neat PHBV to 32.5° for the nanocomposites with 10% CNCs (mass fraction).