Nitrene transfer has become a powerful approach for the installation of nitrogen functionalities, enabling rapid access to structurally diverse molecules. In this study, we report a Co(III)-catalyzed, highly site-selective C5-H amination of thiochromones using anthranils as convenient aminating reagents. This protocol exhibits broad scope with respect to both thiochromone substrates and anthranil coupling partners, delivering the desired products with high levels of regioselectivity. Furthermore, the aminated thiochromone products serve as valuable synthetic intermediates for the further construction of sulfur-containing heterocyclic frameworks.