TiNb₂O₇ materials were synthesized via a microwave‐assisted microemulsion technique and a conventional solid‐state reaction route. Microwave‐assisted microemulsion process produced TiNb₂O₇ powders with small particle sizes (50–100 nm) and increased surface area (22.4 m²/g) in comparison to the samples synthesized from solid‐state method. Micelles in the microemulsion acted as nano‐reactors and confined the grain growth of TiNb₂O₇. The microwave‐assisted microemulsion‐derived TiNb₂O₇ powders presented a high discharge capacity of 333.2 mAh/g at 0.1C. The materials also delivered 94.8% retention at 5C after 100 cycles. The solid‐state derived samples only processed the 283.2‐mAh/g discharge capacity at 0.1C with 83.2% retention at 5C after 100 cycles. The amended capacity and cyclability of microwave‐assisted microemulsion‐derived TiNb₂O₇ resulted from the augmented Li⁺ diffusion and the diminished charge transfer resistance. It was also found that the microwave‐assisted microemulsion‐derived TiNb₂O₇ delivered 208 mAh/g discharge capacity at 10C, which was higher than solid‐state derived samples (92 mAh/g). The improved capacity was owing to the enhancement in pseudocapacitive contribution. Present research indicated that the microwave‐assisted microemulsion method effectively enhanced the electrochemical performance of TiNb₂O₇ powders.