Electrochemical behaviour of some alkaloids, namely: caffeine, aminophylline, theophylline, codeine phosphate and papaverine hydrochloride, that are in solution in various combinations or in the presence of other compounds contained in pharmaceuticals or in real samples (urine) was investigated using cyclic voltammetry (CV), square-wave voltammetry (SWV) and differential pulse voltammetry (DPV) on electrochemically activated glassy carbon electrode. [...] The proposed electroanalytical methods were successfully applied in the simultaneous determination of these alkaloids in different combination or in the presence of other compounds. The great part of these combinations can be analyzed simultaneously because they practically do not interfere. The electrochemical test methods attempted to detect the presence of alkaloids in urine samples collected from subjects who consumed coffee (caffeine), and from a patient under treatment with Miofilin® (aminophylline). Urine samples were determined after filtration, without prior dilution and after dilutiion with acetate buffer at pH 4.5. Best results were obtained using DPV performed on electrochemically activated glassy carbon electrode. Thus in samples taken from subjects who drink coffee the caffeine concentration detected was 6.21×10−7 mol L−1 in the first sample and 7.77×10−7 mol L−1 in the second sample, while aminophylline concentration detected was 1.15×10−7 mol L−1.