A one-pot strategy is employed for facile synthesis of mesoporous LixMnO2 (x = 0.19–0.41) by means of pulse electrodeposition technique. LixMnO2 materials with different chemical and physico-chemical properties are synthetized by modulating the pulse parameters. As results demonstrating, the functional properties of LixMnO2 are deeply influenced by varying both independent parameters namely, ton (time of current applying) and toff (time of current switching off) as well as dependent parameters: duty cycle (θ) and pulse frequency (ƒ). The mesoporous Li0.41MnO2 with a hierarchical morphology of nano-walls and a considerably high BET surface area of 137.49 m2 g−1 is achieved by applying the optimized pulse parameters (ton = 5 ms, toff = 45 ms, duty cycle = 10% and pulse frequency = 20 Hz). The Li0.41MnO2 shows superior performance as cathode material of Li-ion batteries, delivering the first discharge capacity of 284.45 mAh g−1, retaining 94.22% of first discharge capacity after 250 charge-discharge cycles and is still able to deliver 204 mAh g−1 after 110 successive charge-discharge cycles at different C-rates. This work proves that applying a lower duty cycles of pulse current, with optimized value of 10%, leads to the unique featured properties of LixMnO2 which giving rise to superior electrochemical performance.