The tungsten oxide covered tungsten (W) tip of a scanning tunneling microscope was found to act as a catalyst to catalyze the S-H dissociative adsorption of phenylthiol and 1-octanethiol molecules onto a Ge(100) surface. By varying the distance between the tip and the surface, the area of the tip-catalyzed adsorption could be controlled. We have found that the thiol headgroup is the critical functional group for this catalysis and the catalytic material is the tungsten oxide layer of the tip. This local tip-catalyzed adsorption may be used in positive lithographic methods to produce nanoscale patterning on semiconductor substrates.