Electrostatic spray deposition (ESD) technique was used to fabricate thin LiCoO2 layers on a metal substrate. A unique, highly porous structure with a narrow pore-size distribution around 1 mu m was obtained at 230 degrees C using acetates as precursors and a mixture of ethanol (15 vol%) and butyl carbitol (85 vol%) as solvent. The pores were three-dimensionally interconnected. This structure was thermally stable at temperatures up to 600 degrees C. At small flow rates of the precursor solution, a nearly linear relation was found between pore size and flow rate. At deposition temperatures above 230 degrees C the porous structure disappeared. A possible formation mechanism for the porous structure has been proposed.