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Herein, a simple yet efficient hydrothermal strategy is developed to in-situ convert multi-layered niobium-based MXene (Nb2CTx) to hierarchical Nb2CTx/Nb2O5 composite. In the hybrid, the Nb2O5 nanorods are well dispersed in and/or on the Nb2CTx. Thanks to the synergetic contributions from the high capacity of Nb2O5 and superb electrical conductivity of the two-dimensional Nb2CTx itself, the resultant Nb2CTx/Nb2O5 hybrid exhibits excellent rate behaviors and stable long-term cycling behaviors, when evaluated as anodes for Li-ion batteries.