UVPES studies and ab initio and DFT computations havebeen done on the benzene···ICl complex;electronspectral data and computed orbital energies show that donor orbitalsare stabilized and acceptor orbitals aredestabilized due to complexation. Calculations predict an obliquestructure for the complex in which theinteracting site is a CC bond center in the donor and iodine atom inthe acceptor, in full agreement withearlier experimental reports. BSSE-corrected binding energiesclosely match the enthalpy of complexationreported, and the NBO analysis clearly reveals the involvement of theπ orbital of benzene and the σ* orbitalof ICl in the complex.