Surface and interface properties are important in controlling the yield and efficiency of the photochemically initiated immobilization. Using a silane-functionalized perfluorophenyl azide (PFPA-silane) as the photoactive cross-linker, the immobilization of polymers was studied by adjusting the density of the surface azido groups. Dilution of the photolinker resulted in a gradual decrease in the density of surface azido groups as well as the thickness of the immobilized film. When a nonphotoactive silane was added to PFPA-silane, the film thickness decreased more rapidly, suggesting that the additive competed with PFPA-silane and effectively reduced the density of the surface azido groups. The effect of surface topography was studied by adding a nonphotoactive silane with either a shorter (n-propyltrimethoxysilane (PTMS)) or a longer spacer (n-octadecyltrimethoxysilane (ODTMS)). In most cases the long chain ODTMS shielded the surface azido groups, resulting in a more rapid decrease in film thickness as compared to PTMS treated under the same conditions. As the density of the surface azido groups decreased, the immobilized polymer changed from smooth films to patched structures and, eventually, single polymer molecules.