The conventional solid-state reaction suffers from low diffusivity, high energy consumption, and uncontrolled morphology. These limitations are competed by the presence of water in solution route reaction. Herein, based on concept of combining above methods, we report a facile solid-state reaction conducted in water vapor at low temperature along with calcium doping for modifying lithium vanadate as anode material for lithium-ion batteries. The optimized material, delivers a superior specific capacity of 543.1, 477.1, and 337.2 mAh g-1 after 200 and 1000 cycles at current densities of 100, 1000 and 4000 mA g-1, respectively, which is attributed to the contribution of pseudocapacitance. In this work, we also use experimental and theoretical calculation to demonstrate that the enhancement of doped lithium vanadate is attributed to particles confinement of droplets in water vapor along with the surface and structure variation of calcium doping effect.