H+/Li+ ion exchange and structural stability of the high ionic conductivity Nb-doped Zr-garnet Li6.75La3Nb0.25Zr1.75O12 (LLNZO) are investigated in this study. Relationships between ion exchange and Li-population per unit cell, which are necessary to establish the practical framework of garnet electrolytes, are deduced for garnet oxides within ion-exchange process. H+/Li+ ion exchange of cubic LLNZO powder is performed continuously in distilled water and products with various exchange levels are obtained via this simple method. FTIR spectra show the evolution of H-O bonding through the ion-exchange process. A maximum of 74.8% exchange of Li+ by H+ was found, consistent with a preferential replacement of octahedrally coordinated Li. The cubic garnet phase is maintained throughout all levels of proton exchange observed. The formation of garnet-type solid solution of Li6.75-xHx-La3Nb0.25Zr1.75O12 is indicated by well-resolved lattice fringes as well as the linear evolution of crystal lattice parameters with the ion exchange level. The reverse ion exchange of H+ by Li+ is successfully achieved in Li+ containing aqueous solutions, demonstrating its high structural stability and good compatibility for promising applications in lithium batteries. (C) 2015 Elsevier B.V. All rights reserved.