A new green-chemistry strategy, based on modified solid-state reaction with the addition of water vapor to accelerate acid-base reactions (ABR) at low temperature, was developed along with Ca-doping to synthesize electrode material for lithium-ion batteries. The new method which helps in control the particles size and saving energy in synthesis has been developed. To explain this process, we proposed a mechanism in which water droplets play a key role as sub-micro reactors, calculated as few tens of nanometers, to ensure proper reaction conditions and confine crystal growth to nano-dimensions. The synergic effect of the proposed ABR method and Ca-doping is discussed to further explain the increase in the specific surface area and electrochemical performance of the anode material. The optimized material, Ca-doped Li3VO4, delivers a superior specific capacity of 543.1 mAh⸳g-1 after 200 cycles at a current density of 100 mA⸳g-1, which could be attributed to the contribution of pseudocapacitance.