We present a novel process to gain selective deposition and generate high feature edge acuity micropatterns of TiO2 thin films from a gas phase. Self-assembled monolayers (SAMs) of octadecyltrichloro-silane were modified to produce a methyl/silanol pattern and applied as templates to deposit TiO2 through the use of titanium dichloride diethoxide. Patterned SAMs showed high selectivity for nucleation and growth of TiO2, plus a feature edge acuity of the TiO2 pattern well below 2.1%. Moreover, we developed a novel process to realize a two-dimensional arrangement of TiO2 particles onto a SAM from a gas phase.