In this study, we present an inexpensive, stable, and easily available boryl radical source (BPhNa) employed in a Halogen Atom Transfer (XAT) methodology. This mild and convenient strategy unlocks the use of not only alkyl iodides as radical precursors but also of the more challenging alkyl and aryl bromides to generate C-centered radicals. The generated radicals were further engaged in the -Markovnikov hydroalkylation of electronically diverse styrenes, therefore achieving the formation of C(sp)-C(sp) and C(sp)-C(sp) bonds. A series of experimental and computational studies revealed the prominent role of BPhNa in the halogen abstraction step.