Fluorescent switches based on spirocyclic zwitterionic Meisenheimer (SZMC) complexes are stimuli-responsive organic molecules with application in a variety of areas. To expand their functionality, novel switching mechanisms are herein reported for these systems: (a) acid- and redox-triggered formation of an additional protonation state with distinct optical properties, and (b) solvent-induced fluorescence modulation. We demonstrate that these new features, which enable both multistimuli and multistate operation of SZMC switches, can be exploited in the preparation of smart organic materials: wide-range pH optical probes, electrochromic and electrofluorochromic films, and polymer-based fluorescent detectors of organic liquids.