Thin films of poly-[Fe(vbpy)3](PF6)2 formed an electrode surfaces by reductive electropolymerization of [Fe-(vbpy)3](PF6)2(vbpy is 4-methyl-4’-vinyl-2,2’-bipyridine) undergo vbpy displacement with [NEt4]CN in acetonitrile to give poly-[Fe(vbpy)2(CN)2], poly-vbpy. The dicyano films incorporate AgNO2 forming poly-[Fe(vbpy)2(CN)-(CNAg)](NO2), poly-vbpy as shown by FT-IR and XPS. Electrochemical reduction results in the formation of colloidal silver particles dispersed throughout the films. Under potential hold conditions, further aggregation occurs accompanied by diffusion to the film-electrode interface. Incorporation of AgNO2 into films of poly-[Fe(vbpy)3]-(PF6)2 also occurs but by partitioning rather than chemical binding. Electrochemical reduction gives colloidal Ag0. Reduction of either film with AgNO2 in the external solution results in the formation of <0.5 to 2-3 mum sized particles on the film surface as shown by SEM measurements.