We describe a new method for depositing patterned materials, based on non-covalent trapping of ligands in solvent-templated nanocavities created in aromatic, self-assembled monolayer or polymer films. A model has been developed and tested to describe nanocavity formation and the ligand adsorption process, which occurs via ligand exclusion from ambient, aqueous solution into the hydrophobic nanocavities. Ligand adsorption rates and ligand adsorbate reactivity with solution species are governed by ligand size/geometry design factors identified using the model. Spatial control of adsorption is achieved via film photochemical changes that inhibit subsequent ligand adsorption/accessibility (UV or X-ray) or displacement of entrapped ligands (50 keV electron-beam) during film patterning. The reactivity of the adsorbed ligand is illustrated by the selective binding of Pd-II species that catalyze electroless metal deposition. Fabrication of high-resolution (approximate to 50 nm), positive-tone patterns in nickel with acceptable feature-edge acuity and critical dimension control (approximate to 5 %) is demonstrated.