BiVO 4 hollow microspheres have been synthesized in the presence of ethylenediaminetetraacetic acid (EDTA) by a microwave hydrothermal method. The as-prepared hollow microspheres were composed of hundreds of nanorods. Increasing the amount of EDTA produced a new nanocage structure. The evolution process of BiVO 4 with different microstructures indicated that the amount of EDTA added played a crucial role in determining the shape of the samples. Additionally, it was found that the existence of EDTA was vital to mediate the crystal growth, and the hydrothermal time and temperature were key parameters in determining the BiVO 4 morphologies. A possible formation mechanism is proposed.