Ionic conductivity in a compound is rooted in a delicate interplay between its crystal structure and its structural defects (vacancies, interstitials, etc.). Hence, understanding this interplay is of utmost importance to design new solid state electrolytes. To shed some light on the above query, we investigated the rich crystal chemistry of Li6Zn(P2O7)(2). This compound undergoes multiple structural transitions under the influence of temperature, which increases the conductivity by several orders and lowers the activation energy. We explained this jump in conductivity by the increased disorder associated with cation mixing. Our structural exploration indicates that both the room-temperature alpha-polymorph and the high-temperature zeta-polymorph crystallize in a C2/c space group but with a much smaller unit cell volume for the latter. While their structural framework based on P2O74- is similar, the zeta-polymorph presents a fully disordered Li/Zn sublattice, while it is fully ordered for the alpha-polymorph. Furthermore, the bond valence energy landscape calculations show that in the alpha-polymorph, the Li+ conduction is two-dimensional, whereas because of Li+/Zn2+ site mixing, Li+ can hop three-dimensionally in the zeta-polymorph.