This work presents the simultaneous determination of cadaverine, histamine, putrescine and tyramine by square wave voltammetry using a boron-doped diamond electrode. A multivariate calibration method based on partial least square regressions has allowed the resolution of the very high overlapped voltammetric signals obtained for the analyzed biogenic amines. Prediction errors lower than 9% have been obtained when concentration of quaternary mixtures were calculated. The developed procedure has been applied in the analysis of ham samples, which results are in good agreement with those obtained using the standard HPLC method.