Methods for simultaneously increasing the conductivity and the porosity of NiO layers grown by pulsed laser deposition (PLD) were investigated in order to develop improved photocathodes for p-DSSC applications. NiO:Li (20at%) layers grown on c-Al2O3 by PLD showed a sharp drop in conductivity with increasing substrate temperature. Layers grown at room temperature were more than two orders of magnitude more conductive than undoped NiO layers but did not show evidence of any porosity in Scanning Electron Microscope (SEM) images. A new method for imposing a nanoporosity in NiO was developed based on a sacrificial template of nanostructured ZnO. SEM images and EDX spectroscopy showed that a nanoporous morphology had been imprinted in the NiO overlayer after preferential chemical etching away of the nanostructured ZnO underlayer. Beyond p-DSSC applications, this new process could represent a new paradigm for imprinting porosity in a whole range of materials.