The electronic properties of azobenzene (AB) in interaction with gold clusters and adsorbed on the Au(111) surface are investigated by adopting a near-Hartree-Fock-Kohn-Sham (HFKS) scheme. This scheme relies on a hybrid Perdew-Burke-Ernzerhof functional, in which the exact non-local HF exchange contribution to the energy is taken as 3/4. Ionization energies and electron affinities for gas phase AB are in very good agreement with experimental data and outer valence Green's function) calculations. The presence of C-H⋯Au interactions in AB-Aun complexes illustrates the role played by weak interactions between molecular systems and Au nanoparticles, which is in line with recent works on Au-H bonding. In AB-Aun complexes, the frontier orbitals are mainly localized on the gold platform when n ≥ 10, which indicates the transition from a molecular to a semiconducting regime. In the latter regime, the electronic density reorganization in AB-Aun clusters is characterized by significant polarization effects on the Au platform. The accuracy of the near-HFKS scheme for predicting adsorption energies of AB on Au(111) and the interest of combining exact non-local HF exchange with a non-local representation of the dispersion energy are discussed. Taking into account the significant computational cost of the exact non-local HF exchange contribution, calculations for the adsorption energies and density of states for AB adsorbed on Au(111) were carried out by using a quantum mechanics/molecular mechanics approach. The results strongly support near-HFKS as a promising methodology for predicting the electronic properties of hybrid organic-metal systems.