Carbon-coated LiCoPO4 particles are synthesized by one-pot hydrothermal process using three different organic additives (carboxymethylcellulose sodium salt (CMC), glucose, and ascorbic acid). The effect of the organic additives on particle size, morphology, nature of carbon coating, and electrochemical property of the resulting LiCoPO4 is investigated. CMC plays important roles to decrease the particle size and form well-covered carbon coating on the surface. Carbon-coated LiCoPO4 prepared using CMC delivers higher initial discharge capacity of 135 mA h g−1 at 0.1 C, and shows superior rate capability and cyclic performance than the other samples. The improved electrochemical characteristics are attributed to not only the fine particle which allows facile electronic and ionic transport, but also the high coverage of carbon coating which improves the electrical conductivity and prevents the irreversible reactions of the charged LiCoPO4 with electrolyte.