Polymers and metals have been fashioned into functional composites utilized in electronics, product packaging and decorative films despite their disparate mechanical, thermal, and bonding properties. Metallic nanoparticles on polymeric architectures hold potential for catalysis, antimicrobial filtration membranes and solar cells. However, adhesion between polymers and metallic particles is notoriously weak due to the differences in atomic and molecular configuration of these materials; as a result, their functional application can be undermined. Furthermore, the process of delamination of metallic particles on polymeric substrate is exacerbated by the differences in compliance; delamination and has been shown to be dependent on adhered metal particle size. This work explores the adhesion characteristics of electrolessly deposited copper particles on two distinct polymer architectures: thin films and fibers. Polyacrylonitrile was spun-coat into a thin film of a few microns as well as electrospun into a non-woven fiber mat, with fiber diameters on the order of 1000 nm. Catalytic palladium nanocrystals on these structures was achieved via a classical pretreatment processes. Electron microscopy was used to characterize the time evolution of copper particle size as well as distribution. The chemistry as well as crystallography of the fabricated structures were assessed using FT-Infrared Spectroscopy and X-ray Diffraction. Adhesion was measured using a scanning probe nanoindentation tool to perform scratch testing on the metal particle on thin film structure in a constant load scratch test. The adhesion performance as a function of particle size and specific pretreatment is then compared to the delamination of metal particles deposited on the non-woven fiber mats using tensile stretching (by flat punch nanoindentation and mechanical tensile straining). The similarity in the local probe versus the macroscopic behavior allows future adhesion improvements to be quantified using the local probe prior to the more complex non-woven fiber geometry.