The present invention discloses porous fuel cell electrode structures, assemblies, and systems having one or more conformal metallic layers selectively deposited on one or more pore surfaces, as well as to various methods relating thereto. In one embodiment, the present invention is directed to an electrode structure adapted for use with a fuel cell system (e.g., a hydrogen or a direct hydrocarbon fuel cell system), wherein the electrode structure comprises a substrate or support structure having one or more discrete porous bulk matrix regions disposed across a top surface of the substrate. In this embodiment, each of the one or more discrete porous bulk matrix regions is defined by a plurality of acicular pores that extend through the substrate or support structure. The plurality of acicular pores define inner pore surfaces, and the inner pore surfaces have a conformal electrically conductive layer thereon, as well as a plurality of catalyst particles.