For the first time, it is discovered that the calcination products of the mixture containing titanium dioxide (TiO2) and cuprous chloride (CuCl) were a novel kind of anode materials of LIBs. Herein, a mixture containing TiO2 and CuCl with a Ti/Cu mole ratio of 2:1 was calcined at different temperatures in air to harvest the samples. The samples sintered at 350°C, 400°C and 450°C were respectively classified as sample a, b and c. As analyzed, TiO2, CuO and CuCl2 were the principal components of all resultant samples. Interestingly, as compared to the pure TiO2, all prepared samples, especially sample b, delivered a markedly enhanced electrochemical property. For instance, the initial DC (discharge capacity) of sample b at 0.1 A g−1 was 487 mAh g−1, being much better than that of sample a, c and the pure TiO2 (sample o). Impressively, the DC value of sample b was around 101 mAh g−1 at 1.0 A g−1 after 100 cycles, which, respectively, was about 1.5, 2.0 and 5.3 times that of sample a (66 mAh g−1), c (49 mAh g−1) and o (19 mAh g−1). After a thorough investigation, the reduced Rct and the evidently increased DLi+ were considered as the main causes providing all samples, especially sample b, a satisfied electrochemical performance. To summarize, the electrochemical properties of all as-produced samples were better than that of the pure TiO2. That is, a groundbreaking concept, that using a calcination product containing TiO2, CuO and CuCl2 rather than a pure substance as the anode materials of LIBs, was developed here.