In this study, we fabricated nanofibrous foams of neat poly(3-hydroxybutyrate) (PHB) and PHB/cellulose nanocrystal (CNC) nano-composite using nonsolvent-induced phase separation (NIPS) followed by solvent extraction. Two different nonsolvents, tetrahydrofuran (THF) and 1,4-dioxane (Diox), in combination with the solvent, chloroform (CF), were used for NIPS. The parameters of NIPS-derived crystallization kinetics were calculated using Avrami analysis of time-dependent infrared spectral measurements. The lower viscosity and poorer PHB affinity of THF than those of Diox resulted in rapid crystallization and gelation rate, which in turn resulted in higher strength of the foam. The mechanical reinforcement by the incorporation of CNCs was achieved for the composite foam prepared in Diox/CF but not in THF/CF, owing to the relatively better dispersion of the CNCs in Diox than that in THF. A rapid rate of NIPS-derived crystallization and gelation was achieved in THF/CF with the incorporation of CNCs, indicating the effective crystal nucleation of CNCs. However, the presence of CNCs deaccelerated the crystallization in Diox/CF, indicating that the inhibition effect of PHB mobility became more dominant than the nucleation effect of CNCs; this was because the CNC dispersion became more homogeneous in Diox/CF. In vitro cell viability assays exhibited excellent cytocompatibility of the foams, thereby showing potential for use in biomedical applications.