Substitution of iron by other transition metals within the remarkably stable olivine framework is of interest considering the expected gain in energy density. However, manganese rich olivine materials suffer from sluggish redox kinetics, leading to electrochemical performances at high current densities which are below expectations. The source of the kinetic limitations is not clear, with multiple processes having been proposed, including low bulk electronic conductivity, structural instability of Mn3+ and a phase transition mechanism. This study employed 7Li MAS NMR relaxation techniques to indirectly probe Li+ dynamics using various stoichiometry of chemically prepared Li x MnyFe1-yPO4 (0 ≤ (x, y) ≤ 1). Focusing on the particle level, the aim was to understand how the different crystal phases, alongside the Mn structural contribution, influence Li+ transport at each stage of the oxidation process. Significantly, the formation of an olivine solid solution with vacancies within this progression gave rise to a faster 7Li transverse relaxation derived from superior Li+ motion.