Titanium doping in lithium manganese oxide spinels was shown to be beneficial for the structural stability of the potential Li-ion battery cathode materials LiTi x Mn 2−x O 4 , 0.2 ≤ x ≤ 1.5, yet the distribution of Li/Ti/Mn in the structure and the cation oxidation states, both pivotal for the electrochemical performance of the material, are not fully understood. Our work investigates the changes in the local ordering of the ions throughout this series by using a combination of 7Li NMR spectroscopy and ab initio density functional theory calculations. The 7Li NMR shifts are first calculated for a variety of Li configurations with different numbers and arrangements of Mn ions in the first metal coordination shell and then decomposed into Li−O−Mn bond pathway contributions to the shift. These Li−O−Mn bond pathways are then used to simulate and assign the experimental NMR spectra of different configurations and stoichiometries beyond those in the initial subset of configurations via a random distribution model and a reverse Monte Carlo approach. This methodology enables a detailed understanding of the experimental 7Li NMR spectra, allowing the variations in the local ordering of the ions in the structure to be identified. A random distribution of Ti 4+ −Mn 3+/4+ sites is found at low Ti content (x = 0.2); an inhomogeneous lattice of Mn 4+ - rich and Ti 4+ -rich domains is identified for x = 0.4, and single-phase solid solution is observed for x = 0.6 and 0.8. A mixed Li−Mn2+ tetrahedral and Li−Mn 3+/4+ −Ti octahedral configuration is determined for the x = 1.0 case. A specific cation ordering in the partially inverse LiTi 1.5 Mn 0.5 O 4 case is found, which transforms into a two-phase network of disordered Mn 3+ -rich and ordered Mn 2+ -rich domains for x = 1.1−1.4.