We describe a rapid, reliable method of preparing nanoporous Ni or Co films using nanostructured poly(chlorop-xylylene)(nanoPPX) Films as templates. The nanoPPX films are vapor deposited onto Si substrates using oblique angle polymerization (OAP), resulting in the formation of an obliquely aligned PPX nanorod array on the substrate. The nanoPPX films are then subjected to noncovalent functionalization using an aromatic ligand (i.e., pyridine) by means of treatment with either an aqueous solution of the ligand or ligand vapor. The results of quartz crystal microbalance and X-ray diffraction studies Support a model in which pyridine adsorption is facilitated by the formation of pi-pi interactions with aromatic moieties in the amorphous surface regions of nanoPPX. The physisorbed pyridine in the nanoPPX film can subsequently bind a catalytic Pd(II)-based colloidal seed layer. Continuous, conformal Ni or Co films, characterized by FIB/SEM and AFM, are grown oil the Pd(II)-laden nanoPPX Films using electroless metallization, Analogous metallization of a conventionally deposited planar PPX Film results in noncontinuous or patchy metal deposits. Such behavior is attributed to the Sluggish adsorption of pyridine in the planar PPX film, resulting in an similar to 22-fold decrease in the quantity of pyridine adsorbed compared to that in a nanoPPX film. Consequently, the level of Pd(II) bound by pyridine oil a planar PPX film is insufficient to catalyze continuous metallization. Results of a statistical two-level factorial design indicate that the morphology of the metal layer formed oil a nanoPPX Film is profoundly influenced by the ligand adsorption condition (i.e., aqueous ligand vs ligand vapor treatment) and is correlated to the catalytic activity of Co films for the production of hydrogen from sodium borohydride decomposition.