A new method was proposed for the determination of underivatized biogenic amines based on ion-exchange chromatography coupled with mass spectrometry detection. The method was applied to the analysis of 10 biogenic amines in fresh and processed fish products. The amines were extracted from muscle tissue with water without any additional derivative step or sample clean-up. Separation of biogenic amines was done by the IonPac (4 × 50 mm) column, applying a gradient eluent by mixing formic acid (2 mol L⁻¹) and Milli-Q water (formic acid concentration from 400 mM to 2 M). The results demonstrated a linear response in the range of 0.01 to 10 mg L⁻¹. The detection limits for the fish products ranged from 20 ng/g up to around 400 ng/g for histamine and putrescine, respectively. Spermidine and spermine showed significantly higher detection limits. This current method can be used for the determination of biogenic amines in both fresh and processed fish products for regulatory purposes and monitoring food-safety issues relating to these amines, particularly histamine. It is also a useful method for evaluation of other commercial analytical test kits and commonly used methods that are possibly affected by the food matrix due to processing or other drawbacks arising from the derivatization process.