In this study, a gas chromatography–mass spectrometry (GC-MS) method was established for the determination of zearalenone and its five derivatives in feed, including zearalanone, α-zearalanol, β-zearalanol, α-zearalenol, and β-zearalenol. An effective immunoaffinity column was prepared for sample purification, which was followed by the silane derivatization of the eluate after an immunoaffinity chromatography analysis for target compounds by GC-MS. Matrix effects were corrected by an isotope internal standard of zearalenone in this method. The six analytes had a good linear relationship in the range of 2–500 ng/mL, and the correlation coefficients were all greater than 0.99. The limits of detection (LODs) and limits of quantification (LOQs) were less than 1.5 μg/kg and 5.0 μg/kg, respectively. The average spike recoveries for the six feed matrices ranged from 89.6% to 112.3% with relative standard deviations (RSDs) less than 12.6%. Twenty actual feed samples were analyzed using the established method, and at least one target was detected. The established GC-MS method was proven to be reliable and suitable for the determination of zearalenone and its derivatives in feed.