Physico-chemical characterization of the high-silica zeolite catalyst SSZ-74 (ref. 1) suggested that it, like the related materials TNU-9 (ref. 2) and IM-5 (ref. 3), has a multidimensional 10-ring channel system. Such pore systems are ideal for many petrochemical applications, and indeed SSZ-74 has been shown to be a good catalyst for a wide variety of reactions. The elucidation of its framework structure, however, proved to be difficult. Comparable problems were encountered with TNU-9 and IM-5, which were synthesized with related structure-directing agents. Their framework structures, which are the two most complex ones known, both have 24 Si atoms in the asymmetric unit, and were finally solved by combining high-resolution powder diffraction data with information derived from high-resolution electron microscopy images. Therefore, a similar approach, using the powder charge-flipping algorithm to combine the two types of data and molecular modelling to help to locate the structure-directing agent, was applied to SSZ-74. This procedure eventually revealed a most unusual 23-Si-atom framework structure (|(C(16)H(34)N(2))(4)&Si(92)(4)O(184)(OH)(8)]) with ordered Si vacancies.