Oligo(dimethylsiloxane)-based reactive mesogens were prepared and shown to form room-temperature smectic phases which were 'frozen-in' by photopolymerization. Homeotropically aligned, nanostructured thin films were obtained by spincoating, and micropatterning was demonstrated. These hybrid reactive mesogens are suitable for the preparation of aligned nanostructured polymer thin films with potential applications ranging from stimuli responsive coatings to nanoporous membranes.