[2.1.2.1]Metacyclophane ([2.1.2.1]MCP) 3 containing hydroxyl groups at the bridge is obtained by a pinacol coupling reaction using aluminum powder. The Albright-Gordman oxidation of [2.1.2.1]MCP 3 yielded tetracarbonyl derivative 4, and the following condensation reaction of 1,2-phenylenediamine yielded quinoxaline-annulated [2.1.2.1]MCP 5. The UV and fluorescence spectra as well as the influences of an alkali metal ion on the fluorescence spectra of quinoxaline-annulated [2.1.2.1]MCP 5 were reported.