Lithium metal phosphates are amongst the most promising cathode materials for high capacity lithium-ion batteries. Owing to their inherently low electronic conductivity, it is essential to optimize their properties to minimize defect concentration and crystallite size (down to the submicron level), control morphology, and to decorate the crystallite surfaces with conductive nanostructures that act as conduits to deliver electrons to the bulk lattice. Here, we discuss factors relating to doping and defects in olivine phosphates LiMPO₄ (M = Fe, Mn, Co, Ni) and describe methods by which in situ nanophase composites with conductivities ranging from 10⁻⁴–10⁻² S cm⁻¹ can be prepared. These utilize surface reactivity to produce intergranular nitrides, phosphides, and/or phosphocarbides at temperatures as low as 600 °C that maximize the accessibility of the bulk for Li de/insertion. Surface modification can only address the transport problem in part, however. A key issue in these materials is also to unravel the factors governing ion and electron transport within the lattice. Lithium de/insertion in the phosphates is accompanied by two-phase transitions owing to poor solubility of the single phase compositions, where low mobility of the phase boundary limits the rate characteristics. Here we discuss concerted mobility of the charge carriers. Using Mössbauer spectroscopy to pinpoint the temperature at which the solid solution forms, we directly probe small polaron hopping in the solid solution Li_xFePO₄ phases formed at elevated temperature, and give evidence for a strong correlation between electron and lithium delocalization events that suggests they are coupled.