The identification of controlled substances in food matrices is a challenge for forensic laboratories. Classical techniques, such as color tests and thin-layer chromatography, do not provide molecular structural information and cannot be used as a principal means of identification. Infrared spectroscopy (IR) and gas chromatography/mass spectrometry (GC/MS) can identify controlled substances, but suffer from several shortcomings. We describe a UHPLC/MS method for the detection, separation and confirmation of psilocybin and psilocin in mushrooms and chocolate matrices.