The local crystal structures and electronic structuresof LiMxFe1-xPO4 (M = Co, Ni, Rh) are studied through first-principles calculations. The lattice constants and unit cell volumes are smaller for the Co and Ni doped materials than for pure LiFePO4, while larger than for the Rh doped material. The local structures around M atoms in the doped materials are studied in details. The total density of states (DOS) and atomic projected DOS (PDOS) are all calculatedand analysed in detail. The results give a reasonableprediction to the improvement of electronic conductivity through Fe-site doping in LiFePO4 material.