A perfect combination: The association of a chromium(III) trimeric building unit and 1,3,5‐benzenetricarboxylate led to the powdered solid MIL‐100. Simulations provided a crystal structure solution, which matched the experimental powder XRD pattern. This unique simulation/diffraction combination allowed the structure determination of a giant‐pore solid with a zeotype architecture, built up from hybrid supertetrahedra (see picture).