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Conversion‐type transition metal oxide MoO3 has attracted considerable interest as a promising anode material for lithium ion batteries (LIBs), but it suffers from the low electronic conductivity and the large volume changes upon lithiation/delithiation. To overcome these drawbacks, we herein report the full encapsulation of core‐shelled MoO3‐TiO2 into the carbon nanofibers (CNFs) via a facile coaxial electrospinning followed by a two‐step annealing process. TiO2 shells and MoO3 cores were coaxially integrated into the porous CNFs (denote the composite as TiO2/MoO3@CNFs). The two‐step annealing strategy (carbonization in Ar and then oxidization in air) allows the readily encapsulation of MoO3 into CNFs. When applied as anode materials for LIBs, the coaxial TiO2/MoO3@CNFs demonstrate superior lithium storage performance, delivering a high reversible capacity of 561 mAh/g after 300 cycles at 1000 mA/g with a much higher capacity retention of 70.8% than that of the MoO3@CNFs without TiO2 layers (only 42.3%). The results clearly demonstrate that the CNFs matrices and the TiO2 shells together efficiently enhance the electrode conductivity and buffer the volume changes of MoO3 upon cycling. [ABSTRACT FROM AUTHOR]