In this work, we investigate the mode of interaction of a family of fluorescent zinc complexes with HS- and H2S. Different experiments, performed by diverse spectroscopic techniques, provide evidence that HS- binds the zinc center of all the complexes under investigation. Treatment with neutral H2S exhibits a markedly different reactivity which indicates selectivity for HS- over H2S of the systems under investigation. Striking color changes, visible to the naked eye, occur when treating the systems with HS- or by an H2S flow. Accordingly, also the fluorescence is modulated by the presence of HS-, with the possible formation of multiple adducts. The results highlight the potential of the devised systems to be implemented as HS-/H2S colorimetric and fluorescent sensors. Bioimaging experiments indicate the potential of using this class of compounds as probes for the detection of H2S in living cells.