The purpose of this study was to understand the dissolution behavior of maize and potato starches in 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]):water mixtures at room temperature. With an increasing ratio of ionic liquid (IL):water, the long- and short-range ordered structures and granule morphology of both starches were disrupted progressively. The multiscale structure of maize starch was disrupted completely after treatment with the [Emim][OAc]:water mixture of 6:4, indicating good dissolution performance of this mixture for maize starch. This mixture seemed to provide a balance between the viscosity of the solvent and availability of ions to disrupt starch H-bonds. The different dissolution behaviors of maize and potato starches in [Emim][OAc]:water mixtures were attributed to structural differences of the granule surfaces. Our results showed that the dissolution behavior of starches was affected by both starch sources and properties of [Emim][OAc]:water mixtures, which may provide guidance for the development of green technology for processing of biopolymers with low energy consumption.