Different starch properties may cause alterations in the foodstuff’s external appearance. However, modification processes in starches are usually secretive. The use of chemically modified starches is regulated by international standards, which makes it important to identify its presence and type. Mid-infrared spectroscopy (MIR)-modified starches’ identification can be hindered by the presence of excess glucose. This research investigates types of modification in commercial starches and in approaches that circumvent MIR’s limitations with exploratory analysis. It also considers that enzymatic hydrolysis (α-amylase and amyloglucosidase) can highlight the points of modification in the structure, which can be detected with infrared assays. To determine if sour cassava starch (FCS) is modified and check its type, six samples were selected: a native one, three of the most common cassava modified starches (etherified, esterified, and FCS), and two laboratory processed samples (Acid, Oxidized). The results showed that the sour cassava starch showed similarities with a commercial ester and an oxidized cassava starch, which may be due to the formation of a graft, corresponding to what the literature has already reported for corn starch treated with lactic acid and gamma radiation.