Esterification is one of the most important methods to alter the structure of starch granules and improve its applications. Conventionally, starch esters are prepared by conventional or dual modification techniques, which have the disadvantages of being expensive, have regent overdoses, and are time-consuming. In addition, the degree of substitution (DS) is often considered as the primary factor in view of its contribution to estimate substituted groups of starch esters. In order to improve the detection accuracy and production efficiency, different detection techniques, including titration, nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis/infrared spectroscopy (TGA/IR) and headspace gas chromatography (HS-GC), have been developed for DS. This paper gives a comprehensive overview on the recent advances in DS analysis and starch esterification techniques. Additionally, the advantages, limitations, some perspectives on future trends of these techniques and the applications of their derivatives in the food industry are also presented.