We recognized that, in order to truly harness the potential of crosselectrophile coupling, it would be necessary to conceive a new catalytic paradigm that would allow direct coupling of a diverse array of (hetero)aryl electrophiles without involving multiple metal systems to differentiate the reactivity of substrates and/or facilitate the transmetalation step. Visible light mediated excited-state palladium catalysis has the ability to engender hybrid aryl Pd(I)-radical species from respective aryl (pseudo)halides via single electron transfer . During this SET process, the singly occupied molecular orbital (SOMO) of the triplet-excited state [LnPd(0)]* is known to be localized on Pd and stabilized by mixing with the σ* orbital of the CX bond, leading to the rupture of CX bond and the formation of the PdX bond, resulting in the formation of hybrid aryl Pd-radical species . The bond dissociation energy of the CX bond in aryl halides varies significantly from I to Cl . Being the lowest bond dissociation energy of CI bond in aryl iodide, the σ* orbital of the CI bond are lower in energy as compared to aryl bromides and chlorides. As a consequence, the energy gap between the SOMO of the triplet-excited state [LnPd(0)]* and the σ* orbital of the CI bond (LUMO; lowest unoccupied molecular orbital) would be much less, leading to the better mixing of these two orbitals and driving the reaction more efficiently as compared to other aryl halides towards the rupture of the CI bond and the formation of the hybrid aryl Pd-radical species. With this in mind, we hypothesized that this excited-state palladium catalysis could allow us to differentiate aryl (pseudo)halides based on their bond dissociation enthalpy (BDE). Subsequently we questioned if an open-shell Pd-photocatalytic cycle might be merged with Pd-cross-coupling cycle to render a new catalysis paradigm for cross-selective (hetero)biaryl formation by directly utilizing either two different combination of (hetero)aryl halides or a combination of (hetero)aryl halide and triflate. In this context, we envisioned that the relative rate of formation of hybrid aryl Pd(I)-radical species from aryl iodides/triflates and ancillary ligand controlled Pd(II) oxidative addition complex from aryl bromides/chlorides might be a crucial factor to harness the cross-selectivity. On this basis, we herein report the development of a palladium-based new catalytic system for the successful realization of cross-electrophile coupling of (hetero)aryl halides and pseudohalides in the presence of visible light (Fig. ).