A high-performance liquid chromatography tandem mass spectrometry method is described for the simultaneous determination of mycotoxins, including Ergot alkaloids (EAs), in 3 types of grains. The extraction of 23 mycotoxins was evaluated and performed by using a modified QuEChERS-based sample preparation procedure. The proposed method was fully validated on spiked grain samples (barley, wheat and oat) to assess the linearity, limit of detection (LOD) and limit of quantitation (LOQ), matrix effects, precision and recovery. After validation, this method was applied to 143 samples of various types of 3 grains from the Republic of Korea to survey the level of mycotoxin contamination in Republic of Korean grains. A total of 42 grain samples (29%) were contaminated with at least one of these mycotoxins at levels higher than the LOQ. The results demonstrated that the procedure was suitable for simultaneously determining these mycotoxins in cereals and could be performed for their routine analysis in mycotoxin laboratories.