The layer‐by‐layer technique allows to graft molecular monolayers on bulk surfaces that, in turn, allow to graft monolayers of metal nanoparticles. This microreview focuses on the preparation of such materials featuring a monolayer of silver nanoparticles (AgNP) and their use as antimicrobial surfaces against both planktonic bacteria and biofilms. The role of Ag+ release and of direct cell/AgNP contact in the antibacterial action will be stressed as a function of the adhesive molecular layer, of the AgNP dimension and shape, of their surface density, and of the molecular overcoating. While these surfaces display an intrinsic antibacterial action, a further evolution will also be reviewed, in which additional photothermal antibacterial action can be switched on demand, using near‐IR radiation and non‐spherical AgNP or a combination of AgNP with non‐spherical AuNP. The intrinsic and switchable photothermal action of these surfaces will be unraveled, and their synergistic effect stressed.