Vinylarenes represent an important class of core skeleton embedded in natural products, organic materials, and pharmaceutical molecules. Therefore, numerous efforts have been devoted to developing efficient methods for their preparation. Among them, transition-metal-catalyzed oxidative coupling of arenes and alkenes has proved to be a powerful method due to its high atom and step economy. Although a wide range of oxidative alkenylations of arenes have been developed, the alkenes employed in most cases are still limited to electron-deficient alkenes. Reported herein is a Rh(III)-catalyzed C-H cross-coupling of benzoxazinones and simple unactivated styrenes to furnish a variety of vinylarene scaffolds. This established protocol is characterized by wide functional group compatibility, high yields, and excellent regio- and chemo-selectivity. Mechanistic studies and gram-scale experiments on this high-value conversion are disclosed. Moreover, the potential utility of this method was highlighted by a series of further transformations.