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TiNb2O7, as a promising alternative of Li4Ti5O12, exhibits giant potential as low‐temperature anode due to its higher theoretical capacity and comparable structural stability. However, the sluggish electronic conductivity still remains a challenge. Herein, bulk modification of Cu+ doping in porous TiNb2O7 microsphere is proposed via a simple one‐step solvothermal method with subsequent calcination...