Traditional physicochemical and biological techniques, as well as advanced oxidation processes (AOPs), are often inadequate, ineffective, or expensive for industrial water reclamation. Within this context, the electrochemical technologies have found a niche where they can become dominant in the near future, especially for the abatement of biorefractory substances. In this critical review, some of the most promising electrochemical tools for the treatment of wastewater contaminated by organic pollutants are discussed in detail with the following goals: (1) to present the fundamental aspects of the selected processes; (2) to discuss the effect of both the main operating parameters and the reactor design on their performance; (3) to critically evaluate their advantages and disadvantages; and (4) to forecast the prospect of their utilization on an applicable scale by identifying the key points to be further investigated. The review is focused on the direct electrochemical oxidation, the indirect electrochemical oxidation mediated by electrogenerated active chlorine, and the coupling between anodic and cathodic processes. The last part of the review is devoted to the critical assessment of the reactors that can be used to put these technologies into practice.