In this work, the performance of two methods for simultaneous determination of propyphenazone (PRO), paracetamol (PAR), and caffeine (CAF) were compared. One is based on the use of a conventional electrochemical cell (steady‐state condition) and the other on the use of a batch injection analysis (BIA) cell; both systems were associated with square‐wave voltammetric detection (SWV). Three well separated (▵E ≥ 0.25 V) oxidation peaks were obtained for PRO, PAR, and CAF using 0.1 mol L−1 H2SO4 as electrolyte and a boron‐doped diamond (BDD) as working electrode. In addition, the electrochemical oxidation mechanism of PRO is being proposed for the first time. The average relative standard deviations of CB and BIA methods were 4.1 % and 3.1 %, respectively. The conventional system presented better limits of detection and the BIA system a significantly greater throughput (four times faster). Statistical comparison between the results obtained with both proposed methods and those obtained by chromatography was carried out and no significant differences were observed (95 % confidence level).