Dissolution is a ubiquitous process in nature and industry. However, due to technical difficulties, the detailed dissolution process at the nanoscale has seldom been captured experimentally. In this study, we investigated the dissolution dynamics in the confinement of toluene surface nanodroplets on polystyrene (PS) thin films in oversaturated toluene/water mixture solutions. This was achieved by adjusting the immersion durations from several minutes to 9 h. Dissolution takes place upon the deposition of nanodroplets on the PS surfaces, leading to the formation of surface nanostructures. Interestingly, we found that the induced nanostructures underwent complex morphological changes, from complex nanocraters with central bulges and/or multiple rims to simple nanocraters. We speculate that diffusiophoresis plays a key role in the formation of the complex nanocraters, as it facilitates the transportation of dissolved PS molecules inside the nanodroplets. We believe this finding not only enhances our understanding of dissolution dynamics at the nanoscale but also holds promise for applications in dissolution-based nanopatterning.