Polyanionic cathode materials for lithium-ion batteries start to be considered as potential alternative for layered oxide materials. Among them, Li 2 CoSiO 4, characterized by outstanding capacity and working voltage, seems to be an interesting substitute for LiFePO 4 and related systems. In this work, structural and electrical investigations of Li 2 CoSiO 4 obtained by sol–gel synthesis were presented. Thermal decomposition of gel precursor was studied using EGA (FTIR)-TGA method. Chemical composition of the obtained material was confirmed using X-ray diffraction and energy-dispersive X-ray spectroscopy. The morphology of β- Li 2 CoSiO 4 was studied using transmission electron microscopy. High temperature electrical conductivity of Li 2 CoSiO 4 was measured for the first time. Activation energies of the electrical conductivity of two Li 2 CoSiO 4 polymorphs (β and γ) were determined. The room temperature electrical conductivity of those materials was estimated as well.