In this work we demonstrate simple techniques to form well crystallised CuAlO2 powders and thick films from CuO and boehmite or alumina, using a novel molten salt painting process. We examine the formation mechanism using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy and in situ high temperature X-ray diffraction and find that the annealing atmosphere plays a critical role. From this we develop a method to create Cu-Al2O3 conductive metal-ceramic composite materials with novel morphologies via the thermal decomposition of CuAlO2 precursor films.