We report on a rapid and scalable method for the self-assembly of networks of photosensitive silicon nanocrystal (Si-nc) micrograin produced by nanosecond laser fragmentation in water. Electrical conductivity through the long range (> 200 mu m) self-assembled luminescent Si-nc based networks is shown. The process forms stable nanoarchitectures which are compatible with subsequent plasma and heat treatments allowing for the deposition of carbon adatoms on the self-assembled structure. This strategy is environmental-friendly and could be efficiently used to control the complex interactions at the Si-ncs surface promoting the growth of specific nanostructures that in turn would enable the formation of long-ranged assemblies. (C) 2009 Elsevier B. V. All rights reserved.