Silica and silicon structures have been prepared at the sub-micrometer length-scale, using laterally phase-separated thin films of poly(styrene) (PS) and poly(lactic acid) (PLA) homopolymer blends. The selective removal of one polymer and the filling of the released space by silica precursor solution led, after calcination, to silica structures on silicon such as arrays of bowl-shape features or pillars, layers with through or non-through cylindrical holes, which has not been observed for some of them. The control of the morphology of the initial polymer film was a key point to achieve such type of structures. Particularly relevant was the use of solvent vapor annealing (vs thermal annealing) of the initial spin-coated films that favored and stabilized laterally phase-separated morphologies. Characteristic dimension of the domains were shown to be coupled with the thickness of the film, thinner films giving smaller domain sizes. Despite a relatively high incompatibility of the two polymers, a macro-phase separation was prevented in all the studied conditions. Sub-micrometric domains were formed, and for the thinner films, nanometric domains as small as 74 nm in size can be obtained. The silica structures formed by the infiltration of the polymer templates were used as hard masks for the cryogenic etching of underlying silicon. New structured surfaces, arrays of silicon pillars which can be plain or hollow at the upper part or arrays of cylindrical holes were formed. A selectivity as high as 21 was obtained using this type of mask for 1.5 mu m deep holes having a typical diameter of 200 nm.