A series of carbon-coated layered structured Li[Cr x Li(1/3−x/3)Ti(2/3−2x/3)]O2 samples (0.3≤ x ≤0.45) were prepared. Among them, the sample of x =0.4 shows the highest initial reversible capacity of 207mAhg−1 at 30mAg−1 in 2.5–4.4V. The reversible Li-storage capacities for the samples with high x values (x =0.4, 0.45) faded slightly while the samples with low Cr content (x =0.3 and 0.35) showed a capacity increase upon cycling. It was found that the relative intensity ratio of (003) peak to (104) peak (R (003) = I (003)/I (104)) is influenced strongly by x value in as-prepared samples. The samples of x =0.35 and 0.4 turn to a similar structure with low R (003) value during cycling. These phenomena indicate that the cation mixing of Cr3+ in the lithium layer occurs in as-prepared samples and became more significant upon delithiation and lithiation. This is supposed being a necessary process for Cr-based layered structure materials possessing electrochemical reactivates. The occurrence of the cation mixing is beneficial from the local lattice distortion caused by the short-range ordering between Ti and Li. This is supposed to be helpful for the migration of Cr6+ and Cr3+ at tetrahedral and octahedral sites. Different from the case of LiNiO2, the cation mixing is essential for the transport and storage of lithium in the carbon-coated Li–Cr–Ti–O layered compounds.