Spinel LiCrTiO4 is synthesized via sol-gel pretreatment and subsequent solid state reaction at different calcining temperatures. Structural observation and electrochemical evaluation show that 800°C is a suitable calcining temperature for LiCrTiO4 preparation. Compared with samples prepared at other temperatures, LiCrTiO4 formed at 800°C exhibits better electrochemical performance with the capacity retention of 92.2% at 100mAg−1 after 80 cycles. Even cycled at a higher current density of 500mAg−1 in 0.0-3.0V, LiCrTiO4 prepared at 800°C still shows excellent cycling performance with a reversible capacity of 226.7mAhg−1 after 80 cycles. Ex-situ valence analysis reveals that the high lithium storage capacity in LiCrTiO4 between 0.0 and 3.0V is attributed to the reversible redox process of Ti4+/Ti3+ and Cr3+/Cr2+ couples. In addition, quasi zero-strain characteristic of LiCrTiO4 during lithiation is also demonstrated by in-situ and ex-situ structural observations. Therefore, LiCrTiO4 exhibits high structural stability and electrochemical reversibility as anode material for rechargeable lithium-ion batteries.