Electrospinning and dc sputtering techniques were combined for the formation of a variety of nano-to-microscale structures of palladium metal. Polyethylene fibers created by electrospinning were used as templates for the dc sputtering of palladium on top of them. Heating the fibers to 320 °C in air eliminated the central polymer core (fugitive phase) resulting in the formation of open and closed core fibers, depending on the amount of Pd previously deposited. The formation of the structures is best explained as a consequence of sputtering being a line-of-sigh technique. Palladium is preferentially sputtered on top of the fiber part facing the target, resulting in a non-uniform deposition. Furthermore, it is proposed that the deposition of palladium on top of the fibers results in the nucleation of palladium crystals growing outward of the surface and producing interesting nanoscale features observed resembling thorns and scales.