Increasingly abused, 1‐benzylpiperazine (BZP), fenetylline, nicocodeine and nicomorphine are central nervous system stimulants with neurotoxic properties. In recent years, many controlled substance analogs (designer drugs) with a large variety of structures have reached illegal markets, making their identification difficult. This work studies the synthesis of BZP‐d7, fenetylline‐d4, nicocodeine‐d4 and nicomorphine‐d8, as internal standards for use in gas chromatography‐mass spectrometry (GC‐MS) analysis for identification of these controlled substances.