An organoelectrophotocatalytic approach for the C-H silylation of heteroarenes through dehydrogenation cross-coupling with H2 evolution has been developed. The organoelectrophotocatalytic strategy is carried out under a simple and efficient monocatalytic system by employing 9,10-phenanthrenequinone both as an organocatalyst and as a hydrogen atom transfer (HAT) reagent, which avoids the need for an external HAT reagent, an oxidant, or a metal reagent. A variety of heteroarenes can be compatible in satisfactory yields with excellent regioselectivity.