The changes of the morphology during heating and the degree of crystallinity of dry and hydrated starch granules are investigated using second harmonic generation (SHG) based Stokes polarimetry. A spatial distribution of various polarization parameters, such as the degree of polarization (DOP), the degree of linear polarization (DOLP), and the degree of circular polarization (DOCP) are extracted and compared with the two dimensional second harmonic (SH) Stokes images of starch granules. The SH signal from hydrated and dry starch on heating differed significantly in DOLP and DOCP values, indicating that hydrated starch has a greater degree of ultrastructural amylopectin disorder. The detail of denaturation and the phase transition of hydrated starch demonstrate the significant influence of thermal processing.