An unexpected discovery of the novel cyclocondensation reaction of 1,8-diazabicyclo[5.4.0]undec-8-ene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) with alkyl coumarin-3-carboxylates is described. First, an unknown skeleton is generated through the concomitant formation of new nitrogen-carbon and carbon-carbon bonds followed by the oxidation of the intermediate product by the second equivalent of the starting coumarin. Pentacyclic DBN-derivatives exhibit strong fluorescence both in solutions (Φfl∼ 0.6-0.8) and in the solid state, while non-planar DBU-derivatives exhibit strong fluorescence in the solid state only.