Optical and electrical properties of samples with Li1 + xCrxTi2 − x(PO4)3 composition (x = 0, 0.05 and 0.1) prepared by a low temperature sol-gel method have been investigated. XRD and Raman spectroscopy measurements respectively reveal the rhombohedral-Nasicon structure of the grown samples and a disorder of Li+ ions with increasing chromium content. Electrical properties were studied by impedance spectroscopy and both dc and grain boundary ionic conductivity increase with Cr content. A high ionic conductivity value of 1.4·10− 4 S cm− 1 at room temperature and an activation energy of 0.31 eV have been obtained for x = 0.1, which are comparable to those measured in the best ionic conductors reported to date. Photoluminescence and cathodoluminescence spectra indicate that self-trapped excitons and oxygen defects related to the TiO6 octahedra structural units are responsible for the observed luminescence in the visible spectral range, explaining the possible electronic origin of a residual conductivity measured in all the samples. Cr incorporation gives rise to infrared emission bands, attributed to different Cr3 + and Ti3 + intraionic transitions, that may be related to the better grain connectivity achieved by Cr doping.