Five novel dimers in which the steroid cores are bridged by a 6,5,6‐trioxabispiroacetal moiety were synthesized by gold(I)‐catalyzed hydroalkoxylation–hydration of steroid diynediols. The double spiroacetalization proceeded with excellent yield and produced almost exclusively the C2 symmetrical trans diastereomer. A small amount of the cis unsymmetrical diastereomer was isolated only in one case. Density Functional Theory calculations were used to further analyze and justify the population of the diastereomers. Characterization of the obtained dimers was based on combined 1D and 2D NMR techniques. X‐ray diffraction of one of the obtained dimers corroborated the anticipated V‐shaped structure and provided additional structural insights on the crystal network. Unexpectedly, the crystalline array showed interconnected voids, resulting in channels that make this new class of steroid dimers suitable candidates for the development of applications on solid state supramolecular chemistry.