In this work, we report the achievement of a homeotropically (or face-on) oriented bilayer formed by a pair of discotic materials designed with specific properties: selective solubility, adjusted transition temperatures, and room temperature hexagonal columnar liquid-crystalline phase. The homeotropic orientation of the bilayer which is only a few hundred nanometers thick is performed by solution-processed deposition followed by thermal annealing in the geometry of open supported films and is evidenced by X-ray scattering. This represents the first proof of principle of an organic heterojunction based on two oriented columnar liquid crystal layers.