The crystalline phase of poly(lactic acid) (PLA) has crucial effects on its own properties and nanocomposites. In this study, the isothermal crystallization of PLA, triethyl citrate-plasticized PLA (PLA–TEC), and its nanocomposite with chitin nanocrystals (PLA–TEC–ChNC) at different temperatures and times was investigated, and the resulting properties of the materials were characterized. Both PLA and PLA–TEC showed extremely low crystallinity at isothermal temperatures of 135, 130, 125 °C and times of 5 or 15 min. In contrast, the addition of 1 wt % of ChNCs significantly improved the crystallinity of PLA under the same conditions owing to the nucleation effect of the ChNCs. The samples were also crystallized at 110 °C to reach their maximal crystallinity, and PLA–TEC–ChNC achieved 48% crystallinity within 5 min, while PLA and PLA–TEC required 40 min to reach a similar level. Moreover, X-ray diffraction analysis showed that the addition of ChNCs resulted in smaller crystallite sizes, which further influenced the barrier properties and hydrolytic degradation of the PLA. The nanocomposites had considerably lower barrier properties and underwent faster degradation compared to PLA–TEC110. These results confirm that the addition of ChNCs in PLA leads to promising properties for packaging applications.