The selective alkylation of 2‐indolylmethanols with 2‐methyl‐N‐heteroaromatics in the presence of perfluorooctanoic acid is herein demonstrated. This protocol features high regioselectivity, easy availability of raw materials and well tolerance of functional groups. This approach allows the formation of a range of hindered quaternary centers. More importantly, the present method offers efficient ways to introduce biologically important indole and quinoline skeleton into highly complex molecular.