Metal desorption behavior of polyguanamine derivatives having cyclic moieties (c-PGs), with metal-scavenging abilities, organized into molecular films was investigated, and a recovery technique was realized. Cadmium (a toxic metal), palladium (a precious metal), and neodymium (a rare earth metal) were studied, along with sodium (a cationic metal). A monolayer of c-PGs forming on an aqueous metal solution surface effectively scavenges cations from the subphase owing to the relative basicity of the cyclic moiety. X-ray photoelectron spectroscopy revealed that cadmium and palladium (both divalent cations) were desorbed by simple 30-60 min ultrasonication of their Langmuir-Blodgett multilayers. Conversely, the desorption of neodymium, a trivalent cation, was very slow. Sodium, a monovalent cation, was difficult to collect. Its valence and monolayer condensation on the aqueous sodium buffer were remarkable, indicating that coordinated sodium ions escape during the monolayer condensation.