Biogenic amines (BAs) are considered to be important indicators of freshness and quality in food. In this work, an analytical method for analyzing ten underivatized BAs in meat by performance liquid chromatography‐tandem mass spectrometry has been developed. Comparison between ion trap and triple quadrupole as mass analyzers indicated that the latter provides greater sensitivity and selectivity. The range of the correlation coefficients of the calibration curves of the analyzed compounds was 0.987–0.999, and the limits of detection and limits of quantification were in the range of 0.002–0.1 mg l−1 and 0.008–0.5 mg l−1, respectively. Once validated, the method was used to analyze the concentrations of BAs in 16 commercial meat samples, for evaluating the freshness of food through the study of BA indices, i.e. biogenic amine index (BAI) and the ratio spermidine/spermine (SPD/SPE). The results indicated that all the samples were fresh, with a BAI lower than 1.49 mg kg−1 and a SPD/SPE ratio lower than 0.41 in each case. This methodology for testing the freshness of meat has potential for quality control applications along the entire production chain of meat products. Copyright © 2014 John Wiley & Sons, Ltd.