The molecular sieve MCM-22 contains structural features previously unobserved in this class of materials. Its framework topology, derived from high-resolution electron micrographs and refined with synchrotron x-ray diffraction powder data, contains two independent pore systems, both of which are accessed through rings composed of ten tetrahedral (T) atoms (such as Si, Al, and B). One of these pore systems is defined by two-dimensional, sinusoidal channels. The other consists of large supercages whose inner free diameter, 7.1 angstroms, is defined by 12 T-O species (12-rings) and whose inner height is 18.2 angstroms. These coexisting pore systems may provide opportunities for a wide variety of catalytic applications in the petrochemical and refining industries. Another structural feature is an unusual-T-O-T-chain that passes through the center of a modified dodecasil-1H [4(3)5(6)6(3)] cage.