In this study, we developed a selective method for synthesis of multi-substituted quinoline-2-ylphosphonates and quinoline-3-ylphosphonates by copper- or gold-catalyzed reactions of phosphoryl-substituted conjugated ynones with 2'-amino-2,2,2-trifluoroacetophenones. The approach proposed makes it possible to obtain various substituted quinolines in good yields. It is also shown that (4,4,4-trifluoro-3-oxobut-1-yn-1-yl)phosphonate reacts with 2-aminoaryl ketones under non-catalytic conditions with formation of 4-substituted quinoline-2-ylphosphonates in high yields.