The photoisomerization of self-assembled monolayers of azobenzene-containing alkanethiols, as well as of mixed monolayers of these substances with n-alkanethiol spacer molecules on Au surfaces, was studied by photoelectrochemical measurements and surface plasmon resonance spectroscopy. A strong dependence on the molecular structure of the adsorbates was found, specifically on the linker between the azobenzene moiety and the alkanethiol: while molecules with an amide group were photoinactive, those with an ether group exhibited pronounced, reversible photoisomerization in pure and mixed adlayers. Both trans-cis and cis-trans isomerization followed first-order kinetics with time constants that suggest high quantum efficiencies for these processes.