In the entire world, cereals and related foodstuffs are used as an important source of energy, minerals, and vitamins. Nevertheless, their contamination with mycotoxins kept special attention due to harmful effects on human health. The present paper was conducted to evaluate published studies regarding the identification and characterization of mycotoxins in cereals and related foodstuffs by liquid chromatography coupled to (tandem) mass spectrometry (LC-MS/MS) techniques. For sample preparation, published studies based on the development of extraction and clean-up strategies including solid-phase extraction, solid-liquid extraction, and immunoaffinity columns, as well as on methods based on minimum clean-up (quick, easy, cheap, effective, rugged, and safe (QuEChERS)) technology, are examined. LC-MS/MS has become the golden method for the simultaneous multimycotoxin analysis, with different sample preparation approaches, due to the range of different physicochemical properties of these toxic products. Therefore, this new strategy can be an alternative for fast, simple, and accurate determination of multiclass mycotoxins in complex cereal samples.