Choline chloride (ChCl) based deep eutectic solvent (DES), facilitated the regioselective synthesis of (E)-1-(4-phenyl-2-styrylquinolin-3-yl)ethan-1-one (4), and (E)-3-phenyl-1-(4-phenyl-2-((E)-styryl)quinolin-3-yl)prop-2-en-1-ones, (5) from the corresponding 2-amino-5-chloro benzhydrol, (1) in one-pot strategy. The 2-methyl-3-acetylquinoline generated in situ from the 2-amino-5-chloro benzhydrol, (1) and acetyl acetone, (2) via dehydrogenative Friedlander reaction in DES could enable subsequent regio-selective C-2 methyl group sp3 C–H activation and rapid alkenylation with alcohols, (3) to provide the desired (E)-2-styrylquinolin-3-yl)ethan-1-ones, 4 in short reaction time and high yields and purity. Likewise, through the simultaneous C-2 and C-3 sp3 C–H activation with aromatic alcohols, (3) the (E)-2-styrylquinolin-3-yl)prop-2-en-1-ones, (5) formation was carried out in DES in high yields and purity. The physicochemical properties viz., UV/Vis, and fluorescence studies of the synthesized compounds were investigated. The absorption and emission properties of these luminophores are attributable to the presence of auxochromes in the 6-position of quinoline moiety, styryl-functional group at the 2-position, and the enone group at 3-position. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim