Aiming at enhancing the electrochromic properties of anodically colored NiO thin films, lithium doped NiO thin films were grown on FTO/glass substrates, by the pulsed laser deposition (PLD) method. Optimized conditions, namely a room temperature substrate under 10 Pa oxygen pressure were used. Comparison with undoped NiO thin films indicates that lithium doping deteriorates NiO cubic phase (1 1 1) preferred orientation and also induces lattice disorder. The investigation of the electrochromic properties of Li–Ni–O thin films in aqueous liquid electrolyte, 1 M KOH, on the one hand and in hydrophobic lithium conductive ionic liquid, 0.3 M LiTFSI in BMITFSI, on the other hand, demonstrates an improvement in the electrochromic performances with lithium doping. Finally, electrochromic devices built on the association of WO3 and Li–Ni–O thin films and using the above quoted ionic liquid blended with PMMA as electrolyte are reported. Good electrochromic performances and neutral color are shown.