We develop the first method for catalytic, exhaustive ortho-alkoxylation of azobenzene photoswitches. Alkoxylation is known to improve the photoswitch properties that control azobenzenes' success in chemical biology or materials sciences, e.g., better completeness of both E → Z and Z → E photoisomerizations and >100 nm red shift of photoresponse. Our method enables straightforward late-stage diversification of photoswitches with interesting functional handles. We showcase four applications: using it to rationally tune lipophilicity, prepare isotopic tracers for metabolism studies, install full water solubility without ionic charges, and efficiently access previously difficult mixed-substituent photoswitches. We also identified a previously unexplored mixed-substituent tetra-ortho family, difluoro-dialkoxy-azobenzenes, whose photoresponse can outperform previous gold standard' tetrafluoro-, dichloro-difluoro-, and tetrachloro-azobenzenes in significant ways. We thus expect that both the scaffolds we showcase and the method we develop will impact broadly on photochemistry and photopharmacology.