Sour cassava starch (polvilho azedo) is a chemically and enzymatically modified starch with the specific property of expansion in bakery products without the use of any chemical or biological leavening agents. In this work, the cumulative knowledge about sour cassava starch is presented in relation to its physicochemical characteristics, with the purpose of establishing a relation between the application properties and some structural and chemical characteristics in order to design a model of the modified structure of starch and the most important technical variables. Such approach will help to provide some quality standards for future adequate valorization of sour cassava starch, especially with respect to potential use in gluten-free products. This work showed that a good sour cassava starch is significantly different from low expansion cassava starches with respect to pH, acid factor, swelling power, specific volume, and polymerization degree (intrinsic viscosity). These variables could be related to the maximization of sour cassava starch expansion for a future predictive decision analysis about a high quality sour cassava starch to the baking use.