A series of carbon-coated layered structured Li[CrxLi(1/3-x/3)Ti(2/3-2x/3)]O-2 samples (0.3 <= x <= 0.45) were prepared. Among them, the sample of x = 0.4 shows the highest initial reversible capacity of 207 mAh g(-1) at 30 mA g(-1) in 2.5-4.4 V 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 (0 0 3) peak to (1 0 4) peak (R-(0 0 3) = I(0 0 3)II(1 0 4)) 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-(0 (0) (3)) 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. (C) 2007 Elsevier B.V. All rights reserved.