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This work evaluated the ozonation of cassava starch, correlating the process conditions with starch structure and properties. The starch structure was evaluated considering both molecules and granules. Ozonation resulted in an increased number of carbonyl and carboxyl groups with increasing ozone consumption. Moreover, a reduction of large and branched molecules was observed, with the consequent increase of smaller sized molecules. The structural changes significantly influenced the pasting properties, gel texture, water absorption and solubility indexes. As the main result, ozonation improved the hydrogels' texture. The 145.3 mg O3 gstarch−1 sample produced gels ~280% stronger than the native starch. Moreover, the ozonated starch hydrogels maintained their consistency even at acidic conditions – on the contrary to native starch. Finally, the ozonated starch pastes were clearer than native ones. Therefore, ozone processing gives new possibilities for cassava starch application. [ABSTRACT FROM AUTHOR]