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The structural modification of starch improves its physicochemical and functional properties and develops new material. Our study aimed to modify rice starch obtained from three varieties using a solvent-free system involving gulupa seed oil and lipase B from Candida antarctica. We characterized six starches (native and modified), performed a digestibility test, and determined the particle sizes, zeta potentials, and calorimetric differences between the materials. All the starches presented a charged surface between −41.6 and −58.9 mV. The modified starches’ fatty acid profiles changed according to the rice variety used, namely, the proportions of C14, C16, and C18 acids. The modified Clearfield, F60, and Oryzica 1 starches showed fatty acid content increased 85%, 23%, and 73%, respectively. The features presented by the three varieties of starch open up the possibility of their industrial application; furthermore, the starch modification process presents economic and environmental advantages.