The local structure and mobility of lithium ions of the NASICON-type ionic conductor Li1+xAlxTi2–x(PO4)3 (with x = 0.0, 0.1, 0.2, 0.35, 0.5, 0.7 and 1.0), synthesized using conventional solid-state reaction route have been studied with solid-state nuclear magnetic resonance (NMR) techniques. 6Li, 7Li, 27Al, and 31P solid-state NMR experiments have been employed to trace the structural changes with varying cation concentration. The structural evolution and the creation of new Al and P environments with changing cation contents were studied by magic-angle spinning (MAS) NMR measurements. 6Li MAS NMR and 27Al triple-quantum MAS (3QMAS) show high-resolution spectra enabling site assignments and phase-purity inspections. The temperature dependences of 7Li NMR spin–lattice relaxation (SLR) rates for different compositions yield important information on the lithium ion mobility in the systems. Li ion jump rates, the activation energies, and the dimensionality of Li diffusion were deduced from the SLR experiments...