Good cycling stability and high theoretical capacity are provided by Fe2TiO5 (iron titanate) as an electrode material due to its distinct crystal structure and numerous redox couples. The conventional ceramic method successfully and effectively synthesises the material. This study discloses the successful doping and replacement of Ti4+ with Mn4+ in the unit cell of Fe2TiO5 pseudobrookite, resulting in decreased band gap energy and a regular increase in unit cell volume with increased Mn-concentration. Doping improves the overall electrical conductivity due to a higher ratio of Ti3+ to Ti4+ which ultimately boosts the electrochemical performance as an anode in LIBs application. The Fe2Ti1-xMnxO5 (x = 0.2) achieves a high specific surface area of 338.6 m2 g−1 with an average pore size distribution of ∼10 nm, which is beneficial to reduce the Li-ion diffusion path and provides large contact areas between electrolyte and electrode surface. The Fe2Ti1-xMnxO5 (x = 0.2) stays ahead in its electrochemical performance compared to all counter partners delivering 765.6 mAh g−1 of initial discharge capacity and having a capacity retention of 392.3 mAh g−1 after 100 continuous charge discharge cycles at a current density of 100 mA g−1. Additionally, an excellent rate performance of 327.9 mAh g−1 is observed even at 5000 mA g−1. No further capacity fading is noted for another 45 cycles, demonstrating the structural stability of electrode material at variable current densities. The superior electrochemical results of Mn4+ doped Fe2TiO5 manifestly show the possibility of serving as an electrode material for high-performance battery applications.