Abstract-Poly (L-lactic acid) (PLLA) and glucose (Glu) were respectively dissolved in N, N-dimethyl acetamide to prepare solutions. The blends of PLLA and glucose with various ratios were prepared by mixed solution method, and characterized with infrared Fourier transform spectrometry, differential scanning calorimetry, thermal gravity analysis, X-ray diffraction and polarized optical microscopy. The structure, thermal properties and crystallinity of PLLA, glucose and the blends were investigated. The results show that PLLA and glucose in blends are liable to form hydrogen-bonding, and PLLA and glucose are partially compatible. The crystallization of the blends increased with increasing glucose. The addition of glucose can promote thermal degradation of PLLA due to the defect of PLLA crystal caused by glucose impurity or trans-esterification between PLLA and glucose.