Arylazo sulfones have been exploited as photoactivatable substrates for the simultaneous photografting of both aryl and methanesulfonyl groups on a gold surface. The obtained samples have been characterized by different spectroscopic techniques including ellipsometry and electrochemistry, infrared reflection absorption, surface-enhanced Raman spectroscopy, XPS, and AFM. Grafting occurs through a simple N-S cleavage and not, as usually observed with aromatic precursors, by electron transfer.