The F4S=N-Xe---N SF3+ cation has been synthesized as the AsF6- salt by rearrangement of [F3S NxeF]. [AsF6] in N SF3 solvent at 0 degrees C. Deep yellow [F4S=N-Xe---N SF3][AsF6], which crystallized from a N=SF3 solution at -10 degrees C, was characterized by Raman spectroscopy (-160 degrees C) and by single-crystal X-ray diffraction (-173 degrees C). The Xe-N bond length (2.079(3) angstrom) of the F4S=N-Xe---N SF3+ cation is among the shortest Xe-N bonds presently known. The F4S=NXe+ cation interacts with N SF3 by means of a Xe---N donor-acceptor bond (2.583(3) angstrom) that is significantly longer than the primary Xe-N bond (2.079(3)angstrom) but significantly shorter than the sum of the Xe and N van der Waals radii (3.71 angstrom). The F4S=N-Xe---N-SF3+ cation undergoes a redox decomposition in N SF3 at 0 degrees C, forming [F3S(N SF3)(2)][AsF6], cis-N2F2, and Xe, which were characterized by low-temperature Raman spectroscopy in the solid state and by F-19 NMR spectroscopy in N SF3 solvent (0 degrees C). Colorless [F3S(N SF3)(2)][AsF6] crystallized from N SF3 at -10 degrees C and was characterized by low-temperature, single-crystal X-ray diffraction. The S(IV) atom of F3S(N SF3)(2)(+) has long contacts with the N atoms of two N SF3 molecules and a F ligand of a neighboring AsF6- anion. The arrangement of long contacts avoids, to the maximum extent, the F atoms of SF3+ and the nonbonding electron pair situated on the pseudo-3-fold axis opposite the F ligands of SF3+, providing distorted octahedral coordination about the S(IV) atom. Quantum-chemical calculations using MP2, B3LYP, and PBE1PBE methods were employed to arrive at the gas-phase geometries, charges, bond orders, valencies, and vibrational frequencies for F4S=N-Xe---N SF3+ and F3S(N SF3)(2)(+) to aid in the assignments of experimental vibrational frequencies. The F4S=N-Xe---N SF3+ cation expands the known chemistry of the F4S=N-group and is the first example of a N-Xe-N linkage to be structurally characterized by single-crystal X-ray diffraction.