This work presents the synthesis and spectroscopic characterization of novel carboxamido and dicarboxamido 6- N-substituted, 2,6-N, N-disubstituted and 2-N-substituted benzimidazole[1,2-a]quinoline derivatives. Target compounds were prepared by conventional reactions of organic and photochemical synthesis. Acyclic precursors 3, 16 and 24 were prepared by the condensation reaction of the corresponding variably substituted benzaldehyde 2 and 15 with 2-cyanomethyl, and 2-methyl benzimidazole 1 and 23. The cyclic derivatives of benzimidazole[1,2-a]quinolines, 4, 17 and 25, were prepared by the thermal cyclization of the acyclic precursor 3 in sulfolane at 280 °C, and by reaction of the photochemical dehydrocyclization of compound 16 and 24 in ethanol with added iodine by illuminating with UV-Hg lamp of 400 W. Corresponding carboxylic acids 5, 8 i 26 were prepared by acidic hydrolysis of cyano substituted derivatives 4, 17 i 25. In the reaction of carboxylic acids 5, 8 i 26 with thionyl-chloride corresponding acyl halogenides 6, 19 and 27 were obtained. N-carboxamido substituted benzimidazole[1,2-a]quinoline derivatives, 7, 8, 10–14, 20–22 and 28–31 were synthesized in the reacion of benzimidazole[1,2-a]quinoline acyl halogenides 6, 19 and 27 with corresponding amines in dry dichloromethane. The structures of prepared compounds were confirmed by means of 1H and 13C NMR, and characterized by UV/Vis and fluorimetric spectroscopy. The spectroscopic properties of target derivatives 7, 8, 10–14, 20–22 and 28–31 were studied by UV / Vis spectroscopy while the fluorimetric tests were conducted for the three N-substituted piperidinyl derivatives 7, 20 and 28.