The first examples of an oriented periodic mesoporous organosilica (PMO) film, containing a variety of organic groups (ethane, ethene, benzene, thiophene) inside the channel walls, are reported. The mesostructure of the PMO film appears oriented with respect to the surface of the underlying glass substrate. Liquid-crystal topological defects in the precursor gels are replicated in the resulting PMO film and are evident in polarized optical microscopy images, recorded between crossed-polarizers, which show fan-type optical birefringence texture characteristic of the mesostructure.