Micro-probe Raman spectroscopy investigation of LiCoPO4 composite electrodes performed after prolonged cycling in LiPF6 EC/DMC electrolyte solution revealed total structural degradation of the olivine structure of the electrodes. The electrodes cycled in the identical conditions but in the presence of the HF-scavenging glassy fiber (GF) separators retain their olivine structure unchanged. The reasons for this pronounced difference are discussed.