The catalytic dehydrogenation of alcohols is essential for the sustainable production of valuable products. This provides a new strategy for green organic synthesis in chemical industries. Herein, we describe a manganese-based catalytic system that enables the efficient synthesis of C3-alkylated indoles from benzyl alcohols and indoles via the borrowing hydrogen process. Furthermore, dehydrogenative coupling of 2-arylethanols and indoles yields C3-alkenylated indoles. Meanwhile, reacting 2-aminophenethanol instead of indoles can also obtain the corresponding indole products with high selectivity under the same conditions.