The low molecular-mass organic compound 4-nitrophenol is involved in many chemical processes and is commonly present in soils and in surface and ground waters, thereby causing severe environmental impact and health risk. Several methods have been proposed for its transformation (bio and chemical degradation). However, these strategies not only produce equally or more toxic aromatic species but also require harsh operating conditions and/or time-consuming treatments. In this context, we report a comprehensive and systematic study of the electrochemical reduction of 4-nitrophenol as a viable alternative. We have explored the electrochemical reduction of this pollutant over different metallic and carbonaceous substrata. Specifically, we have focused on the use of gold and silver working electrodes since they combine a high electrocatalytic activity for 4-nitrophenol reduction and a low electrocatalytic capacity for hydrogen evolution. The influence of the pH, temperature, and applied potential have also been considered as crucial parameters in the overall optimization of the process. While acidic media and high temperatures favor the clean reduction of 4-nitrophenol to 4-aminophenol, the simultaneous hydrogen evolution is pernicious for this purpose. Herein, a simple and effective electrochemical method for the transformation of 4-nitrophenol into 4-aminophenol is proposed with virtually no undesired by-products.