We provide data on the changes in structure and composition of commercial LiNi0.8Co0.2O2 electrode materials for lithium-ion batteries occurring after surface coating with two types of metal oxides: electrochemically active LiCoO2 and inactive MgO. XRD analysis, SEM images, IR spectroscopy and EPR of low-spin Ni3+ ions were carried out for structural characterisation of coated LiNi0.8Co0.2O2 electrodes. Surface modification with LiCoO2 was found to be a more effective route for improving the cycling stability of LiNi0.8Co0.2O2. The favourable effect of LiCoO2-coating was connected with an enhanced stability of the bulk composition and reduction of electrode/electrolyte interaction.