Synthetic cathinones are a class of designer drugs that have captured the attention of researchers and law enforcement agencies around the world. Driven by heightening legal restrictions, this class of drugs now encompasses a large number of psychoactive substances. The detection and characterization of these drugs is complicated by the ever-growing size of the cathinone family. This has fueled the development of unambiguous identification of these drugs in various matrices. There are, however, very few methods reported for improving presumptive screening of seized materials. In this paper, we evaluate the performance of the standard 63Ni ionization ion mobility spectrometry (IMS) technique for the screening and identification of representative cathinones and associated psychoactive compounds. We discuss the effectiveness of the instrument as a screening tool for cathinones by the analyses of 13 typical cathinone products marketed as “bath salts”. Our results show that the ion mobility spectrometer is an acceptable rapid and efficient screening tool for cathinones, positively detecting at least one cathinone in 77% of the samples tested. In addition, we describe an electrospray ionization (ESI) high performance IMS (HPIMS) method for these compounds. The method offers advantages in direct sample ionization and higher resolution. Mass spectrometry (MS) coupled to the HPIMS technique gives the added benefit of identification of ion peaks in products with mixtures of closely related cathinones.