Submicron films of LiCoO2 have been deposited on silicon and stainless steel substrates using RF sputtering and pulsed laser deposition (PLD). Both films show preferred orientation. RF films have their Li diffusion plane oriented favourably, that is, perpendicular to the surface, while PLD films show a parallel, c-axis orientation. Electrochemical experiments indicate a strong dependence of the intercalation rate on the alignment of the host structure toward the electrolyte solution. Lithographic patterning enhances the inferior intercalation properties of the PLD film on silicon, as does the utilisation of stainless steel substrates.