Transition-metal-free, practical one-pot synthesis of C4-aryl-substituted tetrahydroquinolines from simple anilines and readily accessible propargylic chlorides has been developed. Activation of the C−Cl bond by 1,1,1,3,3,3-hexafluoroisopropanol turned out to be the key interaction, which allowed C−N bond formation under an acidic medium. Propargylated aniline is formed as an intermediate via propargylation, and subsequential cyclization and reduction gave 4arylated tetrahydroquinolines. To demonstrate the synthetic utility, total syntheses of aflaquinolone F and I have been accomplished.