As industrialization advances rapidly in pursuit of refining the quality of human life, there has been a release of organic micropollutants (OMPs) such as pharmaceuticals into various water reserves. This has endangered the ecosystem and the possibilities of water recovery. Commonly used tertiary wastewater treatment technologies have proven to, not under all conditions, be less effective in OMP removal. Hence, Advanced Oxidation Processes (AOPs) have gained attention in the recent past due to their production of reactive oxidative species (ROS) that unselectively degrade OMPs. Photocatalysis (PC), an AOP that uses solar radiation to produce ROS, has been investigated earlier, but shows low efficiency due to fast electron-hole recombination. Photoelectrocatalysis (PEC) is a modified version that additionally uses electrical energy, thereby reducing the recombination and improving the OMP removal efficiency. Bismuth vanadate (BiVO4) photocatalyst has gained importance due to its narrow band gap of 2.4 eV and hence, efficient absorption in visible light spectrum. Thus, this research focused on investigating PEC using BiVO4 electrodes for the removal of OMPs in aqueous solutions. The BiVO4 electrodes were fabricated using dip-coating from 1 to 5 layers, and electrodeposition at -0.2 V and -0.4 V, each at durations of 2, 5, 7, 10 and 15 minutes. They were then characterized using analytical techniques to investigate their structural, optical and optoelectronic properties. Subsequently, all the BiVO4 electrodes were used for the photoelectrocatalytic degradation of Acetaminophen (ACT). The electrodes fabricated by dip-coating were shown to achieve superior degradation efficiencies of ACT of over 99% in 5 hours, due to optimum surface morphology and band gap. It was seen that their varied surface structures played an important role in improving OMP degradation, and compensated for their low average quantum efficiency at 7%, as compared to that of electrodeposition at 14%. Next, the photoelectrocatalytic degradation of multiple OMPs in a solution was studied, and it was determined that although the ROS unselectively targeted all the OMPs, some were degraded quicker than others due to their chemical structure. Scavenging experiments were also carried out that affirmed the role played by ROS in the photoelectrocatalytic degradation of the OMPs. Eventually, the degradation of OMPs in secondary wastewater treatment effluent was conducted to test its usage in purification applications. Overall, PEC using BiVO4 electrodes was found to be feasible and successful in OMP degradation, and has the potential to be developed for usage in environmental remediation strategies like water treatment and recovery.