AbstractAlthough TiNb2O7 is regarded as a fast‐rechargeable lithium‐ion battery (LIB) anode material, the intrinsic poor electrochemical kinetics of TiNb2O7 still dramatically impedes its development. Herein, an ionothermal synthesis‐assisted doping strategy is proposed for the preparation of a new W6+‐doped TiNb2O7 material (Ti0.95W0.05Nb2O7) with nanoporous structure (denoted as NPTWNO). The improved Li+ diffusion coefficient of NPTWNO suggests that the ionic‐liquid‐templated nanoporous architecture improves the Li+ diffusion kinetics. The density functional theory computational study reveals that the doped W6+ successfully boosts the electronic conductivity due to the narrowed conduction‐valance bandgap resulted from charge redistribution, which is reflected by the electrochemical impedance spectroscopy data. With the simultaneously enhanced Li+ diffusivity and electronic conductivity, NPTWNO achieves fast‐rechargeability in LIBs. Therefore, this work indicates the potential of ionothermal synthesis‐assisted doping strategy on energy storage materials and offers NPTWNO material with promising electrochemical performance.