Field experiments were conducted to evaluate the morphology, granule size, fine structure, thermal properties, and pasting properties of starch from a waxy (139) and a non-waxy (297) varieties of proso millet grown in Yulin (YY) and Yangling (YL). Compared with the starches from the two varieties grown in YY, the starches from the two varieties grown in YL exhibited higher relative crystallinities, 1045/1022 cm−1 ratio, and amounts of amylopectin long branch chains (APL) but lower 1022/995 cm −1 ratio, amounts of amylopectin short branch chains (APs), and APs/APL ratios. Starches from YL also synthesized long branch-chain amylopectin to enhance intermolecular interactions and form a stable granular structure, which resulted in increased starch gelatinization temperature, enhanced shear resistance, and reduced setback viscosity. Starch from the waxy (139) variety has good application prospects in the food industry because of its high gelatinization temperature and light transmittance and low setback value, which can be ascribed to its extremely low amylose content, polydispersity index, high molecular weight, and dispersed molecular density. It may serve as a reference for applying proso millet starches in the food industry and developing breeding programs to improve starch quality.