The crystalline structure of sago starch related to the gelatinization characteristics is reported in this chapter, although the sago starch synthesis at the molecular biological level is still under discussion. Sago starch granules are oval with a temple bell-like shape, a mean diameter of 37.59 μm, and exhibit a Maltese cross, indicating the presence of some common internal ordering. Sago starch from its X-ray diffraction pattern shows a peak at around 5.6, 17, 18, and 23° (2θ for Cu Kα), which corresponds to 1.58, 0.521, 0.492, and 0.386 nm, respectively. Sago starch is classified as a C type (a mixture of A type and B type as an accessary), containing slightly higher content of B type in the basal portion of sago palm trunk. Low viscosity of sago starch amylopectin is explained by the presence of smaller molecule with a slightly higher number of long chains than the high-viscosity amylopectin. The gelatinization temperature and enthalpy of sago starch determined by a differential scanning calorimeter (DSC) are 69.4-70.1 °C and 15.1-16.6 J g −1 , depending on the moisture content, degree of a crystallinity within the granule, granule size, and the amylose to amylopectin ratio. The observation of granular birefringence (Maltese cross) under polarized light is one of the useful tools to determine the gelatinization behavior of sago starch.