This paper deals with the coupling of polystyrene to a closely packed and highly ordered cationic vinylbenzyl silane (CVBS) on mica. It is shown that a thermal treatment is required for maximum retention of polystyrene on treated mica. Moreover, a thermal treatment at 250°C is much more effective than one at 170°C. The effect of the number of silane monolayers on mica was investigated. In general, one monolayer of CVBS gave optimum retention of polystyrene. The addition of peroxides further improved this retention and at the same time allowed the use of lower treatment temperatures. Some data are presented which consider the importance of the silane solution concentration and silane functional groups.