The cubic garnet-type solid electrolyte Li7La3Zr2O12 with aliovalent doping exhibits a high ionic conductivity, reaching up to ∼10−3 S/cm at room temperature. Fully understanding the Li+ transport mechanism including Li+ mobility at different sites is a key topic in this field, and Li7−2x−3yAlyLa3Zr2−xWxO12 (0 ≤ x ≤ 1) are selected as target electrolytes. X-ray and neutron diffraction as well as ac impedance results show that a low amount of aliovalent substitution of Zr with W does not obviously affect the crystal structure and the activation energy of Li+ ion jumping, but it does noticeably vary the distribution of Li+ ions, electrostatic attraction/repulsion, and crystal defects, which increase the lithium jump rate and the creation energy of mobile Li+ ions. For the first time, high-resolution NMR results show evidence that the 24d, 96h, and 48g sites can be well-resolved. In addition, ionic exchange between the 24d and 96h sites is clearly observed, demonstrating a lithium transport route of 24d−96h− 48g−96h−24d. The lithium mobility at the 24d sites is found to dominate the total ionic conductivity of the samples, with diffusion coefficients of 10−9 m2 s−1 and 10−12 m2 s−1 at the octahedral and tetrahedral sites, respectively.