The effect of PVA fiber volume on the bending toughness of Polyvinyl Alcohol Fiber Engineered Cementitious Composite (PVA-ECC) was mainly investigated. Under the volume contents of 0%, 0.5%, 1.0%, 1.5% and 2.0%, the compressive strength of PVA-ECC and its bending properties based on the square plate method were measured respectively. The mechanism of PVA fiber in ECC was analyzed, and the energy of PVA-ECC square plate was evaluated. The results show that the change of PVA fiber volume fraction has little effect on the compressive strength of ECC material. The increase of PVA fiber volume fraction has little effect on the initial crack load of ECC specimen in the square plate bending toughness test, but the peak load is obviously increased, the mid-span deflection is obviously increased and the crack width is reduced. The bending toughness of PVA-ECC square plate increases with the increase of PVA fiber volume fraction and the toughening effect is the best if the volume fraction is 2.0%．