The invention discloses a method for simultaneously detecting seven fungal toxins in original auxiliary materials of baijiu. According to the method, an improved QuEChERS method is adopted for extraction, further purification is not needed, high performance liquid chromatography is utilized for achieving separation of the fungal toxins, combined quadrupole-electrostatic field orbitrap mass spectrometry (Q-Orbitrab) is achieved, efficient parent ion selectivity and high-resolution accurate molecular weight (The mass number can be accurate to five digits after the decimal point.) are combined, accurate qualitativeness and quantification of the fungal toxins in baijiu and the original auxiliary materials can be achieved, and quantification is conducted through a matrix external standard method. The fungal toxins can be completely and effectively separated within 9 min, the linear relation of the fungal toxins within separate linear response ranges is good, the correlation coefficient R<2> is larger than 0.999, the lowest limit of quantification is lower than 1.0 microgram/L, the lowest detection limit is lower than 0.1 microgram/L, the recovery rate ranges from 70% to 120%, and the relative standard deviation (RSD) ranges from 0.5% to 4%. Compared with the national standard method, the method has the advantages of being rapid, simple, convenient, economical, efficient, safe and the like and can be suitable for separation and quantitative determination of various fungal toxins in baijiu and original auxiliary material samples.