A new sol-gel synthetic route was developed to prepare single-phase phospho-olivines LiMPO4 (M = Fe or Mn), potential cathode materials for the next generation of Li-ion secondary batteries. Triethyl phosphite was used as phosphate organic precursor, with absolute ethanol as solvent. The sol-gel synthesis ensures homogeneity of the precursors at the nanometric scale and improved reactivity, allowing to obtain very small agglomerates and crystal grain size. Several carbon sources were used in order to improve the electrochemical performances of the samples. Galvanostatic cycling tests of the cathodic materials were made on coin cells with Li metal as anode in order to study the influence of the synthesis and the structural-morphological characteristics on the electrochemical performance of the phosphate/C composite.