A new approach for the selective electroless (EL) metallization of surfaces is described. Surfaces are modified with a chemisorbed ligand-bearing organosilane film, and then catalyzed with an aqueous Pd(II) catalyst solution. The catalyzed substrate is then immersed in an EL metal deposition bath to complete the metallization process. The ligating surfaces are produced by molecular self-assembly of 2-(trimethoxysilyl)ethyl-2-pyridine (PYR) on silicon or silica substrates. The catalyst consists of chloride-containing aqueous Pd(II) solutions buffered at pH 5.0 to 6.4; oligomeric chloro and/or hydroxo-bridged Pd(II) complexes act as the catalytic species at the surface. The activity of the catalyst has been characterized and modeled as a function of solution pH, [CI-], and time from preparation. Adhesion of the Pd(II) EL catalyst to the substrate involves covalent bond formation with the surface ligand. An average minimum Pd(II) level on the surface of approximately 10(15) Pd atom cm2 is shown to be necessary to initiate EL metallization of the substrate with an EL Co bath. This process involves fewer steps and displays improved selectivity compared to processes that involve a conventional Pd/Sn catalyst. Fabrication of high resolution metal patterns using the new metallization chemistry in conjunction with deep UV patterning of PYR films is demonstrated.