Various 5,7-bis(trifluoroacetyl)-8-quinolylamines, sulfides and ethers were synthesized in excellent yields by aromatic nucleophilic N-N, N-S and N-O exchange reactions of N,N-dimethyl-5,7-bis(trifluoroacetyl)-8-quinolylamine with amines, thiols and alcohols. Base-catalyzed cyclization of the resulting benzyl 8-quinolyl sulfide and subsequent dehydration gave fluorine-containing thieno[3,2-h]quinolines in high yields.