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 Pmn21 (no. 31) with refined unit cell parameters of a = 13.6738(8) Å, b = 5.0216(3) Å, and c = 25.4883(7) Å (V = 1750.1 Å3). Electron diffraction and transmission electron microscopy confirm the space group and the topology of the structure viewed along the  direction. Solid-state 29Si 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.