Single molecule fluorescence detection of barium is investigated for enhancing the sensitivity and robustness of a neutrinoless double beta decay (0νββ) search in 136 Xe, the discovery of which would alter our understanding of the nature of neutrinos and the early history of the Universe. A key developmental step is the synthesis of bariumselective chemosensors capable of incorporation into ongoing experiments in high-pressure 136 Xe gas. Here we report turn-on fluorescent naphthalimide chemosensors containing monoaza-and diaza-crown ethers as agents for single Ba 2+ detection. Monoaza-18-crown-6 ether naphthalimide sensors showed sensitivity primarily to Ba 2+ and Hg 2+ , whereas two diaza-18-crown-6 ether naphthalimides revealed a desirable selectivity toward Ba 2+ . Solution-phase fluorescence and NMR experiments support a photoinduced electron transfer mechanism enabling turn-on fluorescence sensing in the presence of barium ions. Changes in ion-receptor interactions enable effective selectivity between competitive barium, mercury, and potassium ions, with detailed calculations correctly predicting fluorescence responses. With these molecules, dry-phase single Ba 2+ ion imaging with turnon fluorescence is realized using oil-free microscopy techniques. This represents a significant advance toward a practical method of single Ba 2+ detection within large volumes of 136 Xe, plausibly enabling a background-free technique to search for the hypothetical process of 0νββ.