There are no documented electroanalytical methods for quantifying the anti-inflammatory drug bumadizone (BUM) in pharmaceutical or biological matrices. So, a new voltammetric method was developed to determine BUM at nano concentrations in pharmaceutical forms, in the presence of its alkaline degradant, and in biological fluids. Five electrodes were tested, including three nano-reduced graphene oxide (nRGO) electrodes (5%, 15%, and 20%), a carbon paste electrode (CPE), and a 10% nRGO-modified CPE. The 10% nRGO-modified electrode showed the best performance, offering high selectivity and low detection limits, with good linearity in the concentration range of 0.9 × 102 to 15 × 102 ng mL−1. Differential pulse voltammetry successfully applied this electrode for BUM determination in various samples, achieving excellent recovery without preliminary separation. The method was validated according to ICH guidelines and compared favorably to the reference method. Its environmental impact was assessed using AGREE and Eco-scale metrics in addition to the RGB algorithm, showing superior greenness and whiteness profiles due to safer solvents and lower energy consumption, along with high practical effectiveness using the BAGI metric.