The LiCoPO4 (LCP) is a member of the lithium transition metals phosphates family, recognized as cathode material for lithium ion batteries. This material exist in three different polymorphs: LCP-Pnma (olivine structure), LCP-Pn21a and LCP-Cmcm (Na2CrO4-type structure). The occurrence of phase transitions from Pn21a to Pnma and from Cmcm to Pnma polymorphs after annealing procedures is an evidence of metastable behaviour of two polymorphs. However, a precise study of the magnetic structure of the LCP-Pn21a and LCP-Cmcm polymorphs is still unknown. Previous, the results of the magnetic susceptibility as a function of temperature indicates a paramagnetic Curie-Weiss behaviour at high temperatures and show a long-range antiferromagnetic order below TN= 11 K for LCP Cmcm and Pn21a samples.