The composites of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with different microcrystalline cellulose (MCC) contents were prepared by a solvent casting method. The effects of MCC on the thermal properties of PHBV were studied by TGA and DSC. The DSC results showed that the melt crystallization temperature of the PHBV/MCC increased from 41.9 °C for PHBV to 59.8 °C for the composites containing 20 wt. % MCC, which indicated that the crystallization of PHBV became easier with the addition of MCC. It also illustrated that the MCC could be used as an effective nucleation agent for the crystallization of PHBV. Moreover, it was found that the thermal stability of the PHBV/MCC composites increased compared with the neat PHBV.