Diphosphines displaying azobenzene scaffolds and the corresponding bis-gold chloride complexes have been prepared and fully characterized by photophysical, spectroscopic and X-ray diffraction studies. DFT calculations provide complementary information on their electronic, structural and spectroscopic properties. Comparative investigations have been carried out on compounds featuring phosphorus functions in the meta- and para-positions, respectively, with respect to the azo functions, as well as on diphosphines with an ortho-tetrafluoro substituted azobenzene core. The effects of the substitution patterns on structural and spectroscopic properties are discussed.