The importance of nitrite ions has long been recognized due to their extensive use in environmental chemistry and public health. The growing use of nitrogen fertilizers and additives containing nitrite in processed food items has increased exposure and, as a result, generated concerns about potential harmful health consequences. This work presents the development of an electrochemical sensor based on graphene/glassy carbon electrode (EGr/GC) with applicability in trace level detection of nitrite in water samples. According to the structural characterization of the exfoliated material, it appears as a mixture of graphene oxide (GO; 21.53%), few-layers graphene (FLG; 73.25%) and multi-layers graphene (MLG; 5.22%) and exhibits remarkable enhanced sensing response towards nitrite compared to the bare electrode (three orders of magnitude higher). The EGr/GC sensor demonstrated a linear range between 3 × 10−7and 10−3M for square wave voltammetry (SWV) and between 3 × 10−7and 4 × 10−4M for amperometry (AMP), with a low limit of detection LOD (9.9 × 10−8M). Excellent operational stability, repeatability and interference-capability were displayed by the modified electrode. Furthermore, the practical applicability of the sensor was tested in commercially available waters with excellent results.