An effective and practical strategy has been established for the direct and site‐selective arylation of indoles at the C4 and C5 positions with the aid of a readily accessible, cheap, and removable pivaloyl directing group at the C3 position. This transformation shows good functional‐group tolerance and could serve as a powerful synthetic tool for the synthesis of medicinally relevant compounds. This method and those developed in previous research together enable the regiocontrolled direct arylation of indole at each C−H bond without prefunctionalization of the reactive sites. Grand Slam: An effective and practical strategy has been established for the direct site‐selective arylation of indoles at the C4 or C5 position (see scheme) by the use of a readily available and removable pivaloyl directing group (DG) at the indole C3 position. Now the direct site‐selective arylation of indoles at any given C−H bond is possible by the appropriate choice of this or a previously developed complementary method.