We have developed the domino elimination-rearrangement-addition reaction of N-alkoxy(arylmethyl)amines using organo-lithium and magnesium reagents for the first time. This newly found domino reaction consists of three types of reactions: elimination of alcohol, rearrangement of the aryl group, and addition of either an organo-lithium or a magnesium reagent. The -branched arylamines readily prepared by this domino reaction are widely found as a core structure in pharmaceuticals. This domino reaction was successfully applied to the synthesis of galipinine and martinellic acid. Furthermore, very efficient synthesis of N-(diallylmethyl)arylamines was achieved via domino reactions involving addition-elimination-rearrangement-addition reactions of oxime ethers with allylmagnesium bromide.