A Cp*RhIII-catalyzed efficient synthesis of isoquinolin-3-ol derivatives bearing a pyridinyl ring using imidate as a directing group under C–H activation strategy with pyridotriazoles as carbene reagents is reported. In this reaction, cascade C–H activation, regioselective cyclization, and elimination occur in one pot. The present methodology featured a good range of functional group tolerance and furnished the target products in moderate-to-excellent yields.