Disposal of palm oil mill effluent (POME), which is highly polluting from the palm oil industry, needs to be handled properly to minimize the harmful impact on the surrounding environment. Photocatalytic technology is one of the advanced technologies that can be developed due to its low operating costs, as well as being sustainable, renewable, and environmentally friendly. This paper reports on the photocatalytic degradation of palm oil mill effluent (POME) using a BiVO4 photocatalyst under UV-visible light irradiation. BiVO4 photocatalysts were synthesized via sol-gel method and their physical and chemical properties were characterized using several characterization tools including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), surface area analysis using the BET method, Raman spectroscopy, electron paramagnetic resonance (EPR), and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). The effect of calcination temperature on the properties and photocatalytic performance for POME degradation using BiVO4 photocatalyst was also studied. XRD characterization data show a phase transformation of BiVO4 from tetragonal to monoclinic phase at a temperature of 450 °C (BV-450). The defect site comprising of vanadium vacancy (Vv) was generated through calcination under air and maxima at the BV-450 sample and proposed as the origin of the highest reaction rate constant (k) of photocatalytic POME removal among various calcination temperature treatments with a k value of 1.04 × 10−3 min−1. These findings provide design guidelines to develop efficient BiVO4-based photocatalyst through defect engineering for potential scalable photocatalytic organic pollutant degradation.