Electrochemical treatment systems have the unique ability to completely mineralize poly- and perfluoroalkyl substances (PFASs) through potential-driven electron transfer reactions. In this review, we discuss the state-of-the-art on electrooxidation of PFASs in water, aiming at elucidating the impact of different operational and design parameters, as well as reported mechanisms of PFAS degradation at the anode surface. We have identified several shortcomings of the existing studies that are largely limited to small-scale laboratory batch systems and unrealistic synthetic solutions, which makes extrapolation of the obtained data to real-world applications difficult. PFASs are surfactant molecules, which display significant concentration-dependence on adsorption, electrosorption, and dissociation. Electrooxidation experiments conducted with high initial PFAS concentration and/or in high conductivity supporting electrolytes likely overestimate process performance. In addition, the formation of organohalogen byproducts, chlorate and perchlorate, was seldom considered. Nevertheless, the first step toward advancing from laboratory-scale to industrial-scale applications is recognizing both the strengths and limitations of electrochemical water treatment systems. More comprehensive and rigorous evaluation of novel electrode materials, application of scalable proof-of-concept studies, and acknowledgment of all treatment outputs (not just the positive ones) are imperative. The presence of PFASs in drinking water and in the environment is an urgent global public health issue. Developments made in material science and application of novel three-dimensional, porous electrode materials and nanostructured coatings are forging a path toward more sustainable water treatment technologies and potential chemical-free treatment of PFAS-contaminated water.