Ultrathin layer chromatography (UTLC) is a relatively new variant of thin layer chromatography, with a 10mum thick monolithic silica sorbent layer that gives faster separations with lower limits of detection and reduced analyte and solvent volumes. We have produced UTLC plates with controllable nanostructure and thickness, and show that the layer separation characteristics depends on the film nanostructure. We also show that layers made with in-plane anisotropic nanostructures will exhibit a decoupling effect, where the analyte spots do not develop in the same direction as the solvent front movement. The added layer morphology and material selection adds a degree of freedom to UTLC, and may have applications in multi-dimensional TLC.