The diclofenac (DCF) electrochemical oxidation mechanism was studied through: linear voltammetry (LV), chronoamperometry (CA) sampled-current voltammetry (SCV), potentiostatic coulometry (PC) cyclic voltammetry (CV) under stagnant conditions and linear voltammetry under forced convection conditions (FCLV) over a carbon paste electrode (CPE) from an aqueous medium containing 0.1 M phosphate buffer at pH 7. It was found that the DCF electrochemical oxidation involves an EC mechanism, where the electrochemical reaction is carried out through a one electron-exchange while the chemical reaction involves breaking up the DCF through the nitrogen atom, thereby generating the fragments 2,6 dichloroaniline and 2-(2hydroxyprop-2-enyl) phenol. Reverting the potential scan in the cathodic direction at different scan rates and regardless of its rate, after the oxidation peak, it was found that it was possible to reduce only 38% of the DCF oxidized. The spectrophotometric study carried out during different macro-electrolysis periods allowed observing that the current decrease of the oxidation peak coupled to the DCF absorption (at 270 nm), together with the development of a new spectrophotometric absorption maximum (450 nm), all confirm the EC mechanism proposed. With the use of several experimental techniques (CA, LV and FCLV) and theoretical ones using the Stokes-Einstein approach, the DCF diffusion coefficient was determined, this being in average 8.1 x 10(-6) cm(2) s(-1). (C) 2016 Elsevier Ltd. All rights reserved.