A Rh(III)-catalyzed selective coupling of N-methoxy-1H-indole-1-carboxamide and aryl boronic acids is reported. The coupling is mild and efficient toward diverse product formation, with selective C鈥揅 and C鈥揅/C鈥揘 bond formation. Kinetic isotope effects studies were conducted to reveal a mechanism of C鈥揌 activation and electrophilic addition.