A Co(II)-salen based fluorescent sensor (1.Co) that can selectively recognize cyanide anions in 1:2 binding stoichiometry over other anions has been developed. 1.Co displayed fluorescence enhancement upon the addition of cyanide owing to the interruption of photoinduced electron transfer from the coumarin fluorophore to the cobalt(II) ion. A general regression method was developed to calculate the binding constants in the 1:2 binding system, through which the 1:2 binding between 1.Co and cyanide anions was estimated to be in the range of micromolar dissociation constants.