For the first time, a series of TiO2 complex flakes with edged-curled derived from MAX (denoted as TOC) are successfully prepared through simple and practical cold-quenching pretreatment in liquid nitrogen combined with thermal treatment of MAX flakes etched for various hours and peeled off. When investigated as anodes in lithium ion batteries (LIBs), compared with other TLC-TOC flakes tested, TLC-TOC24 electrode presents the highest discharge capacity in the second cycle of 559.4 mAh g−1 and more than 94% of the capacity after 835 cycles at 0.1 A g−1. When the applied current is changed to 3 A g−1, the reversible specific capacity of TLC-TOC24 remains 150 mAh g−1 after 10000 cycles. Such an excellent cyclic stability is predominantly ascribes to the highway applied by meso/micro-pores for electroactive ions migration, the existence of Al element is benefit for obtaining mesoporous TLC-TOC24 with high specific capacitance. Furthermore, the pseudocapacitive behavior of TLC-TOC24 also remarkably breaks the dynamic ceiling effect of the solid-state diffusion process. Therefore, because of the simplicity, operability and industrialization of cold quenching technique in liquid nitrogen and outstanding electrochemical performance, mesoporous TLC-TOC24 is expected to become negative material for LIBs.