Maleimide-based fluorophores have been effectively employed as bio-probes due to their attractive photophysical attributes, such as small size, high responsivity, and high reactivity while being non-invasive. However, their applicability in the biosystems has been limited due to the fluorescence quenching, caused by the interactions with the polar protic solvents. Therefore, this work is focused on improving the fluorescence in polar media through chemical modifications. For this purpose, the maleimide was functionalized with electron-withdrawing groups, which led to an increased fluorescence efficiency in the solution-state by reducing the interaction with protic solvents; and in the solid-state through the suppression of stacking interactions, thus providing a dual-state emission mechanism. Furthermore, the maleimide derivatives were successfully used as ligands to develop the fluorescent half-sandwich transition metal complexes, thus expanding the scope for their use as hybrid probes. Additionally, the coordination of maleimide-based chromophores to the lanthanide metal ions enhances their luminescence, by overruling the ligand-to-metal charge transfer state with ligand-centered transitions.