A "turn on" fluorescent and colorimetric sensor, HAT(CN)6, was developed for the light-up detection of cyanide. It was implemented through its strong anion-π interaction, inducing thermal CN- → HAT(CN)6 electron transfer, to give the dianion product [HAT(CN)6]2-, which exhibits unexpected fluorescence. The sensor shows high selectivity, rapid response and a low detection limit towards CN- in aqueous solution, hence indicating its enormous potential in practical applications.