LiFeP2O7 and Li0.9Fe0.9Ti0.1P2O7 were synthesised by solid-state reaction and ceramics were sintered. The structure of compounds was studied in the temperature range 300–700 K by X-ray diffraction. Ceramics’ surfaces were investigated by scanning electron microscope. Binding energies of Fe 2p, P 2p and O 1s core levels at ceramics’ surfaces have been determined by X-ray photoelectron spectroscopy and different valence states of Fe and P were detected. Elemental compositions of the compounds were studied by energy dispersive X-ray spectrometer. Impedance spectroscopy was performed in the frequency range 10 Hz–3 GHz and in the temperature interval 400–700 K. The changes of the activation energy of ionic conductivity at 528 and 550 K for LiFeP2O7 and Li0.9Fe0.9Ti0.1P2O7, respectively, were found. The phenomena can be related to disordering in the unit cells of the compounds.