LiCoPO4 (LCP) is a promising candidate as alternative cathode for high-voltage lithium-ion batteries. However, its practical electrochemical performances are still far from the theoretical data likely due to the low electronic and ionic conductivities. Moreover LCP typically suffers a rapid capacity fading upon cycling, probably due to structural degradations and electrolyte decomposition at 5V vs. Li+/Li. Previous studies showed that carbon coating and metal doping may improve LCP electrochemical properties. In this work we report: (a) the fine tuning of a novel synthetic route at low temperature to obtain micrometric LCP crystallites morphologically homogeneous and crystallographically pure; (b) the analysis of the effect of iron doping on LCP structural features and electrochemical properties in lithium cell; (c) the beneficial simultaneous effect of iron doping and post-synthesis high-temperature annealing on the electrochemical performances in Li cells. The optimized material shows a reversible capacity of 120mAhg−1 at 0.1C rate and a capacity retention of 78% after 20 cycles.