Summary Authenticating the adulteration of sweet potato starch with other large‐scale‐produced commercial starches is an urgent matter to control the qualities of sweet potato starch and its related foods. This study discussed the application of small‐angle X‐ray scattering on authenticating the adulteration of sweet potato starch with cassava starch, maize starch and rice starch. Rice starch had a similar thickness of semi‐crystalline lamellae but cassava starch and maize starch exhibited different thicknesses of semi‐crystalline lamellae compared with sweet potato starch. The thickness of semi‐crystalline lamellae of mixed starches changed depending on the proportion of sweet potato starch ( X ) and obeyed the functions of Thickness = −0.01633 X + 11.39637 (sweet potato starch‐cassava starch) and Thickness = −0.01768 X + 11.5631 (sweet potato starch‐maize starch), respectively. These functions were then verified and confirmed their potential in the adulteration of sweet potato starch with cassava starch and maize starch but not rice starch.