Monoclinic BiVO 4 with multiple morphologies and/or porous structures were fabricated using the hydrothermal strategy. The materials were characterized by means of the XRD, Raman, TGA/DSC, SEM, XPS, and UV-Vis techniques. The photocatalytic activities of the BiVO4 materials were evaluated for the degradation of Methyl Orange under visible-light irradiation. It is observed that pH value and surfactant exerted a great effect on the morphology and pore structure of the BiVO 4 product. Spherical BiVO 4 with porous structures, flower-cluster-like BiVO 4 , and flower-bundle-like BiVO 4 were generated hydrothermally at 100°C with poly(vinyl pyrrolidone) (PVP) and urea (pH = 2) and at 160°C with NaHCO 3 (pH = 7 and 8), respectively. The PVP-derived BiVO 4 showed much higher surface areas (5.0–8.4 m 2 /g) and narrower bandgap energies (2.45–2.49 eV). The best photocatalytic performance of the spherical BiVO 4 material with a surface area of 8.4 m 2 /g was associated with its higher surface area, narrower bandgap energy, higher surface oxygen vacancy density, and unique porous architecture.