Tailored organoporous materials-the organic counterparts to inorganic nanoporous materials-have been prepared by a design strategy based on the observation that guanidinium organosulfonates (C(NH2)(3)+RSO3-) crystallize predictably in layered structures. The extension to disulfonates is shown to produce, among others, the motif shown in the Figure (the ovals are organodisulfonate pillars and the rectangles, guests).