This work compared the molecular structures and physicochemical properties of starches obtained from chalky and translucent kernels of six rice cultivars. Starch samples were prepared according to a modified alkali steeping method. Crystallinity, pasting characteristics, and thermal properties were studied by X-ray diffraction, rapid viscosity analysis, and differential scanning calorimetry, respectively. Starch molecular size fractions (amylopectin, amylose, and intermediate material) were estimated by high-performance size exclusion chromatography, and the chain length profiles of isoamylase-debranched amylopectin were evaluated by high-performance anion-exchange chromatography with pulsed amperometric detection. Starches from chalky kernels contained less amylose (more amylopectin) and more short branch-chain amylopectin (less long branch-chain amylopectin) compared with the translucent kernel starches. Differences in starch structural features significantly correlated with observed variation in grain translucency, starch X-ray diffraction patterns, thermal properties, and pasting characteristics. Starch synthesis in chalky kernels may slightly favor glucan chain branching over chain elongation.