The synthesis and fluorescence properties of highly substituted bicyclic pryridine derivatives are described. 2-Substituted-4-oxo-pyrido[2,3-d]pyrimidines 2–8resulted from the acylation reaction of α-aminonicotinonitrile 1with aroyl chlorides, diethyl malonate, morpholine-4-carboxylate, acetic anhydride or formic acid under solvent-free conditions. [4 + 2] Cyclocondensation and cycloaddition reactions of compound type 1with formamide and ammonium thiocyanate tolerated the fused pyrimidines 9and 11, respectively. Finally, the Friedländer-like reaction was applied for the synthesis of 1,8-naphthyridines 12–15via reaction of compound 1with cyclohexanone, dimedone, acetyl acetone and benzyl methyl ketone, respectively, under AlCl3catalysis. The fluorescence spectroscopic data of compounds 1–4, 6–8, 11, 12, 14and 15measured and significant results were observed.