A one-pot strategy for iron-catalyzed C2,3-H arylphosphorylation of electron-deficient quinoxalines with phosphines and aryl compounds is reported. The proposed method features the use of non-noble metal catalysts, the capacity of utilizing multiple aryl compounds as substrates, the simultaneous formation of C-P and C-C bonds in one pot, the simplicity of its operation, the mildness of the reaction conditions, and its compatibility with a wide range of substrates. Moreover, it offers a practical route for direct access to 2-aryl-3-phosphino N-heteroarenes, a class of potential cyclometalated C^N and N^P bidentate ligands that are difficult to prepare with existing C(sp2)-H functionalization methods.