A tetragonal argyrodite with >7 mobile cations, Li7Zn0.5SiS6, is experimentally realized for the first time through solid state synthesis and exploration of the Li-Zn-Si-S phase diagram. The crystal structure of Li7Zn0.5SiS6 was solved ab initio from high-resolution X-ray and neutron powder diffraction data and supported by solid-state NMR. Li7Zn0.5SiS6 adopts a tetragonal I4 structure at room temperature with ordered Li and Zn positions and undergoes a transition above 411.1 K to a higher symmetry disordered F43m structure more typical of Li-containing argyrodites. Simultaneous occupation of four types of Li site (T5, T5a, T2, T4) at high temperature and five types of Li site (T5, T2, T4, T1, and a new trigonal planar T2a position) at room temperature is observed. This combination of sites forms interconnected Li pathways driven by the incorporation of Zn2+ into the Li sublattice and enables a range of possible jump processes. Zn2+ occupies the 48h T5 site in the high-temperature F43m structure, and a unique ordering pattern emerges in which only a subset of these T5 sites are occupied at room temperature in I4 Li7Zn0.5SiS6. The ionic conductivity, examined via AC impedance spectroscopy and VT-NMR, is 1.0(2) × 10-7 S cm-1 at room temperature and 4.3(4) × 10-4 S cm-1 at 503 K. The transition between the ordered I4 and disordered F43m structures is associated with a dramatic decrease in activation energy to 0.34(1) eV above 411 K. The incorporation of a small amount of Zn2+ exercises dramatic control of Li order in Li7Zn0.5SiS6 yielding a previously unseen distribution of Li sites, expanding our understanding of structure-property relationships in argyrodite materials.