The study of the complexation of 3,3-diphenyl-3H-benzo[f]chromenes containing an aza-15-crown-5-ether or morpholine units with Mg2+, Ba2+ and pb(2+) in acetonitrile are reported. The spectroscopic and kinetic behaviour of the photomerocyanine isomers of these chromenes is strongly affected by complexation with metal cations. In order to interpret the experimental data, a formation of anion-"capped" complexes was supposed.