In this paper, the electrochemical response of chloramphenicol (CHL) was investigated on a bare glassy carbon electrode (GCE) and after modification with reduced graphene oxide (GCE/rGO). Preliminary studies by cyclic voltammetry demonstrated an adsorption-controlled mass transport regime of CHL species and a pH-dependent behavior on both electrode surfaces. An adsorptive stripping differential pulse voltammetry (AdSDPV) method was proposed and under optimized instrumental conditions, a comparison of the analytical characteristics of both sensors was performed. The GCE/rGO sensor showed an increase in sensitivity (10-fold), and an anticipation of the reduction potential (200 mV), compared to the bare electrode, due to the adsorptive character (pre-concentration of the CHL species) and the electrocatalytic effect of the nanomaterial. The method was applied to skimmed and whole milk samples, which were simply diluted (50-fold) in supporting electrolyte. The results by AdSDPV using GCE/rGO showed adequate detectability (0.22 μmol L⁻¹), good precision with a 6% relative standard deviation (RSD) and satisfactory recovery ranging from 93 to 108%. The obtained results were statistically similar (95% confidence level) with those performed through ultra-fast liquid chromatography (UFLC). Furthermore, the sensor showed an improvement in the analytical performance for CHL detection, when compared to other sensors reported in the literature. Therefore, the developed method is reliable and promising for implementation in monitoring CHL residues in milk samples.