A　suitable　protocol　for　the　photocatalytic　decarboxylation　of　carboxylic　acids　was　developed　with　metal-free　ceramic　boron　carbon　nitrides　(BCN).　With　visible　light　irradiation,　BCN　oxidize　carboxylic　acids　to　give　carbon-centered　radicals,　which　were　trapped　by　hydrogen　atom　donors　or　employed　in　the　construction　of　the　carbon-carbon　bond.　In　this　system,　both　(hetero)aromatic　and　aliphatic　acids　proceed　the　decarboxylation　smoothly,　and　C-H,　C-D,　and　C-C　bonds　are　formed　in　moderate　to　high　yields　(35　examples,　yield　up　to　93%).　Control　experiments　support　a　radical　process,　and　isotopic　experiments　show　that　methanol　is　employed　as　the　hydrogen　atom　donor.　Recycle　tests　and　gram-scale　reaction　elucidate　the　practicability　of　the　heterogeneous　ceramic　BCN　photoredox　system.　It　provides　an　alternative　to　homogeneous　catalysts　in　the　valuable　carbon　radical　intermediates　formation.　Moreover,　the　metal-free　system　is　also　applicable　to　late-stage　functionalization　of　anti-inflammatory　drugs,　such　as　naproxen　and　ibuprofen,　which　enrich　the　chemical　toolbox.　©　2021　American　Chemical　Society.