The exotic characteristics of nanoscopic metallic materials bestows diverse functionalities that are increasingly being utilized for a broad range of applications. Polymer substrates present robust architectures for nanoparticle anchoring as well as modulating attendant size-induced aggregation. However, in principle, interfacial adhesion of a polymer-metal material system is weak, making the susceptibility to delamination a challenge. We have deposited copper particles on model polymer thin film and fibrous architectures to study adhesion behavior on these distinct geometries. The average sizes of copper nanoparticles deposited on electrospun fibers for metallization times of 3 and 5 minutes were 13 and 10 nm, whereas the metal island sizes under same metallization times on thin films was 79nm and 81nm. Scratch tests using a nanoindentation system were unable to generate macroscopic film delamination, but did exhibit apparent removal of individual particles, with adhesion forces of 14.9μN, 36μN, and 28.8μN obtained for films metallized for 1, 3, and 5 minutes respectively. Macroscopic tensile testing of fiber mats showed the metallization maintains conformity with the polymer ligament, albeit, with intermittent fracture of the conformal metal coating, signifying substantial adhesion exists between the metallic layer and the PAN fiber.