Correlations between the ionic conductivity and antisite disorder in low cost cathode materials (1D Li+ conducting LiFePO4 and quasi-1D LiFeSO4F) and the origin of the experimentally observed drastic conductivity enhancement in nanoscale heterostructures LixFePO4:Li4P2O7 are explored by molecular dynamics (MD) simulations with a novel bond valence (BV) based force-field. Compared to bulk values, ionic conductivity in surface-modified LixFePO4 is enhanced by up to 3 orders of magnitude. Details of dynamic ion transport pathways are extracted by our BV transport pathway analysis applied to MD simulation trajectories. Besides heterogeneous doping by the redistribution of mobile ions across the interface, ion mobility varies as quantified via the extension of unoccupied accessible pathway regions. A layer-by-layer analysis indicates a maximum mobility close to the interface, but Li+ mobility remains enhanced even at the center of the simulated nanocrystals. Li+ diffusion in LiFeSO4F exhibits a pronounced anisotropy with a “superionic” zig–zag pathway parallel to  involving partially occupied Li sites. A notable long range ion diffusion rate can be maintained in macroscopic LiFeSO4F crystals due to the moderate activation energy for migration perpendicular to the channels.