Nanostructured parallelly oriented TiO2 micropillar arrays, either pure or implanted on a carbon matrix, are prepared via controlled oxidation of hybrid carbonaceous systems. Mild oxidation at 500 °C (O2 1%) leads to formation of parallelly oriented elongated TiO2 pillars, which emerge from a compact α-C phase (TiO2/C composite). Under strong oxidation conditions (O2 10%) formation of pure TiO2 pillar arrays is observed. The pillars constituted of partially cemented anatase or anatase/rutile nanoparticles.