The synthesis, structure solution, and characterization of the high-silica molecular sieve CIT-5 (California Institute of Technology Number 5) is described. CIT-5 is synthesized at hydrothermal conditions in the presence of N(16)-methylsparteinium and preferrably lithium cations. The structural solution of CIT-5 shows that it contains one-dimensional pores circumscribed by 14 tetrahedral atoms (14 MR), Rietveld refinement of the synchrotron X-ray powder data gives a symmetry and space group assignment for the structure of Pmn2(1) (no. 31) with refined unit cell parameters of a 13.6738(8) Angstrom, b = 5.0216(3) Angstrom, and c 25.4883(7) Angstrom (V = 1750.1 Angstrom(3)). Electron diffraction and transmission electron microscopy confirm the space group and the topology of the structure viewed along the [010] direction. Solid-state Si-29 NMR spectroscopy results are consistent with the space group assignment. The thermal/hydrothermal stability of CIT-5 compares well to that of other large- and extra-large-pore, high-silica molecular sieves, The acid form of CIT-5 is able to perform hydrocarbon reactions such as cracking and alkylation and shows behaviors that are different from other zeolites.