The development of molecular and supramolecular optical devices for sensing ionic analytes in solution has emerged as a promissory field in the last decades. In this context, qualitative and quantitative analysis of metal cations based on chromogenic and fluorogenic chemosensors are particularly attractive, especially due to their successfully employment for biological and environmental purposes. In this work, the literature data associated to quinoxaline-based derivatives as chemosensors for metal cations in solution are comprehensively reviewed. Sensing mechanisms, detection limits, solvent effect, work concentration ranges, as well as examples of practical implementation are presented. We believe that the data compilation and pertinent discussion present in this survey should be of interest for researchers of heterocyclic-based chemosensors’ field.