The electrochemical activity of the olivine type $LiMPO_4$ (M=transition metals) cathodes strongly depends on various factors, e.g., the transition metal element M, perturbative doping of the supervalent cations into Li site, composite formation with conductive additives, state of charge/discharge, and particle size and its geometries, etc. This is, therefore, an important issue of interdisciplinary between electrochemistry and solid state science towards practical applications. In order to shed light on this interesting but complicated issue with the transport properties and crystallographic aspects, systematic discussion will be made with the review of our recent publications; (1) first principle derivation of the electronic structures, (2) crystallographic mapping of the selected solid solutions, (3) quantitative elucidation of the electron-lattice interaction, (4) spectroscopic detection of the local environment with Mossbauer and EXAFS, (5) synthetic optimization of the electrode composite, and (6) electrochemical evaluation of the reaction kinetics, particularly on M = Fe, Mn.