Vacuum ultraviolet (VUV, lambda = 172 nm) patterning of alkyl monolayer on silicon surface has been demonstrated with emphasis on the diffusion of VUV induced oxygen-derived active species, which are accountable for the pattern broadening. The VUV photons photo-dissociates the atmospheric oxygen and water molecules into the oxygen-derived active species (oxidants). These oxidants photo-oxidize the hexadecyl (HD) monolayer in VUV irradiated regions (Khatri et al., Langmuir. 24 (2008) 12077), as well as the little concentration of oxidants diffuses towards the masked areas. In this study, we performed VUV patterning at a vacuum pressure of 10 Pa to track the diffusion pathways for the oxidants with help of gold nanoparticles (AuNPs; phi = 10 nm) immobilization. At VUV irradiated sites AuNPs are found as uniformly distributed, but adjacent to the pattern boundary we observed quasi-linear arrays of AuNPs, which are determined by diffusion pathways of the oxidants. The diffusion of oxidants plays vital role in pattern broadening. The site selective anchoring of AuNPs demonstrates the utility of VUV photons for the construction of functional materials with microstructural architecture. (C) 2009 Elsevier B. V. All rights reserved.