Herein, vibrational circular dichroism (VCD) measurements were carried out to study the kinetics of cold-crystallized poly(D-lactide) (PDLA) at the molecular level via qualitative analysis. The amplification of the VCD signals from intra- and inter-chain chiral interactions suggests the formation of partially ordered PDLA, followed by heterogeneous nucleation for crystallization. These results were further supported by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and Fourier transform infrared (FTIR) spectroscopy analyses.