Considering the lack of information on simultaneously removing multiple pharmaceuticals from water or wastewater by electrochemical methods, this study aimed to investigate the removal of multiple pharmaceuticals by electro-coagulation and electro-oxidation based on two types of electrodes (aluminum and graphite). The synthetic wastewater contained a nonsteroidal anti-inflammatory drug (diclofenac), a sulfonamide antibiotic (sulfamethoxazole) and a β-blocker (atenolol). The pharmaceutical removal with electro-oxidation was much higher than those with the electro-coagulation process, which was obtained from a five-cell graphite electrode system, while the removal of pharmaceuticals with aluminum electrodes was about 20% (20 µM). In the electro-coagulation system, pharmaceutical removal was mainly influenced by the solubility or hydrophilicity of the compound. In the electro-oxidation system, the removal mechanism was influenced by the dissociation status of the compounds, which are attracted to the anode due to electrostatic forces and have a higher mass transformation rate with the electro-oxidation process. Therefore, atenolol, which was undissociated, cannot adequately be eliminated by electro-oxidation, unless the electrode’s surface is large enough to increase the mass diffusion rate.