A one-pot three-component approach for the synthesis of 2-(piperidin-1-yl) quinoline based 1,2,4-triazolo[1,5-a]quinoline derivatives (4a–l) has been described by the reaction of aldehyde (1a–f), methyl 2-cyanoacetate (2) and enaminones (3a–b). Different regioselectivities of the reaction are attained with different catalysts and the highest regioselectivity is achieved by L-proline. This new procedure provides an efficient method to construct fused tricyclic heterocycles containing 1,2,4-triazole analogues. In this regard, we have used the least amount of amphoteric catalyst, like L-proline, ammonium acetate and a mixture of pyrolidine with acetic acid, to obtain the 1,4-dihydroquinoline derivative 5a as a by-product. The salient features of this protocol are the mild reaction conditions, high yield (75–85%) and higher regioselectivity toward the desired products 4a–l. The structures of the title compounds were confirmed by FT-IR, ¹H NMR, ¹³C NMR and mass spectrometry.