Synthesis and binding studies of a new calixarene-based fluoroionophore were made. Calix[4]azacrown having an anthracenyl unit displayed large chelation-enhanced fluorescence effects with Cs(+), Rb(+), and K(+) over other metal ion tested. Interesting "molecular taekwondo" processes between Cs(+)-Cu(2+) and Cs(+)-Ag(+) pairs were monitored via fluorescent changes.