Using self-assembled monolayers of the alkanethiol hexadecanethiol as a resist, ultraviolet photolithographic techniques were employed to fabricate arrays of electrodeposited silver on polycrystalline and single-crystal gold substrates. Growth of electrodeposited silver was used as a method of visualizing the photodefined domains. Domain definition was strikingly weaker on the single-crystal surface. This result is attributed to the increased thiolate and silver ion surface mobility expected on a single-crystal surface lacking significant defects or pinning sites.