A high-silica zeolite (Si/Al = 7.1) with the STI framework topology, denoted TNU-10, has been synthesized in the presence of 1,4-bis(N-methylpyrrolidinium)butane and Na+ cations as structure-directing agents, and its structure in the proton form has been refined against laboratory powder X-ray data in space group Fmmm (a = 13.533(1) Å, b = 17.925(2) Å, c = 17.651(2) Å). The space group symmetry is supported by electron diffraction and energy minimization studies. The as-made and proton form of TNU-10 are extensively characterized by elemental and thermal analyses, scanning electron microscopy, N2 adsorption, multinuclear solid-state NMR, IR, and temperature-programmed desorption of ammonia, and the location of the organic structure-directing agent in the channel system is determined by molecular modeling. The catalytic properties of H-TNU-10 and Co-TNU-10 are evaluated for the skeletal isomerization of 1-butene to isobutene and the selective reduction of NO with methane, respectively. When compared to H-ferrierite, a low selectivity to isobutene is observed for H-TNU-10. However, it is found that Co-TNU-10 exhibits a maximum NO conversion of 93% at 823 K under conditions of high concentrations of methane (16000 ppm) and water vapor (10%) and in the presence of 2.6% O2, which is considerable higher than even the value (74%) obtained from Co-ferrierite, known as the best catalyst for this reaction, under the identical conditions.