In this work, we describe the use of hydridosilanes for the attachment of polymer monolayers to SiO2 surfaces. In one approach, first a benzophenone group containing hydridosilane is self-assembled on the SiO 2 surface followed by photochemical attachment of polymer chains deposited onto the monolayer. In a second approach an ATRP initiator is self-assembled to the substrate surface, again using hydridosilane anchor groups. The surface-attached initiator groups are subsequently used for the growth of surface-attached polymer chains in a surface-initiated polymerization reaction. It is shown that, while chlorosilanes require rather stringent exclusion of moisture during self-assembly, the hydridosilanes are rather robust and functional monolayers are formed even under ambient conditions. That in turn allows for the use of silanes in standard printing processes. In contrast to printing of chlorosilanes, which must be carried out under strictly anhydrous conditions, printing of hydridosilanes thus represents a simple and versatile technique for the generation of microstructured surfaces. © 2008 American Chemical Society.