Ti-doped LiMn1.8Ti0.2O4 and LiMnTiO4 spinel materials as cathode for Li-ion batteries are synthesized by solvothermal method using ethylene glycol as solvent. Structural and morphological features of spinel materials are evaluated with X-ray diffraction, field emission scanning electron microscope, and high-resolution transmission electron microscope techniques. Energy-dispersive X-ray and X-ray photoelectron spectroscopy analyzes confirm the presence of different elements in the Ti-doped spinel. Electrochemical Li insertion properties are evaluated by potentiostatic and galvanostatic modes between 1.5 and 4.8 V versus Li/Li+ where the Ti-rich LiMnTiO4 (Mn/Ti = 1) exhibits high specific capacity of 173 mAh g−1 after 50 charge/discharge cycles compared to LiMn1.8Ti0.2O4 (Mn/Ti = 9, 132 mAh g−1) with less Ti content. The titanium-rich LiMnTiO4 exhibits a well-defined voltage profile, higher specific capacity, and enhanced electrochemical performance over Ti-poor LiMn1.8Ti0.2O4 which could be attributed to high microstructural stability of Mn cations with suppressed Jahn–Teller distortion and facilitation of Mn2+/Mn4+ redox couple during the electrochemical charge/discharges.