An efficient and practical strategy for the construction of pyrrolo [3,4-c]isoquinolines via Rh(III)-catalyzed cascade C−H activation and subsequential annulation process from easily available O-methyl aryloximes and maleimides has been disclosed. This facile protocol does not require any inert atmosphere protection with good efficiency in a low loading of catalyst and exhibits good functional group tolerance and broad substrate scope. Notably, the as-prepared products show potential photophysical properties.