New dimeric steroids in which two 5-oxo-4,5-seco-3-yne steroids units are linked by a flexible diyne spacer, were prepared by both Eglinton and Pd-catalyzed coupling of the corresponding monomers. X-Ray crystallography shows that one of the obtained dimers displays a novel supramolecular network in which the facial hydrophobicity of the steroidal skeleton plays an important role. The crystal packing is dominated by interactions that accommodate the steroid cores in a highly crowded packed columnar self-assembly. Unambiguous NMR characterization of the obtained compounds is also provided.