A　visible-light-induced　protocol　has　been　developed　for　the　construction　of　C(sp2)─P　bonds　with　heterogeneous　boron　carbonitrides　(BCN).　The　system　features　with　broad　scope　and　mild　reaction　conditions,　providing　various　aryl　phosphates　in　moderate　to　good　yields　from　arenes　and　aryl　halides.　Mechanism　studies　verify　a　radical　process,　and　C─H　bond　cleavage　is　not　involved　in　the　rate-determined　step.　Furthermore,　the　strategy　allows　the　late-stage　phosphonation　of　biologically　active　compounds　and　facilitates　gram-scale　synthesis,　which　offers　a　metal-free　arene　for　valuable　phosphorus-containing　compounds.　©　2024　Wiley-VCH　GmbH.