Semiconductor ZnO aerogels were synthesized by a sol-gel process with different concentrations (2.5-7.5 wt.%) of Al (n-type) or Na (p-type) and dried under supercritical CO 2 . The materials were calcined at 500 °C to remove the organic content and to crystallize the ZnO. The microstructure of the ZnO-based aerogels comprises a porous structure with hexagonal and platelet-shaped interconnected particles. The bandgap of the aerogels doped with Al decreased significantly compared to pure, undoped ZnO aerogels, while their specific surface area increased. For the electrical characterization of the ZnO-Na/ZnO-Al junctions, the doped ZnO aerogels were deposited on commercial glass substrates coated with indium tin oxide (ITO) by drop casting method. The I-V curves of the p-n homojuntions revealed a characteristic diode rectifying behavior.