In this study, the analytical characterization of three cathinones and one N-pyrrolidinyl-substituted amphetamine derivative is described: 1-([3,4-methylenedioxyphenyl])-2-(propylamino)butan-1-one (N-propyl norbutylone 1), 1-([3,4-methylenedioxyphenyl])-2-(butylamino)butan-1-one (N-butyl norbutylone 2), 2-(benzylamino)-1-phenylheptan-1-one (N-benzyl norheptedrone 3), and 1-(1-[3,4-dimethoxyphenyl]propan-2-yl)pyrrolidine (N-pyrrolidinyl-3,4-DMA 4). The identification was based on ultra-high-performance liquid chromatography-quadrupole time-of-flight-mass spectrometry (UHPLC-QTOF-MS), gas chromatography-orbitrap MS (GC-Orbitrap-MS), nuclear magnetic resonance spectroscopy (NMR), and Fourier transform infrared (FT-IR). GC-Orbitrap-MS, with higher mass accuracy, benefit more on the accurate structure elucidation of product ions compared with the low-resolution GC-MS. The collision-induced dissociation (CID) and electron ionization (EI) pathways of these compounds were examined to assist forensic laboratories in elucidating the structure of new psychoactive substances (NPS) with similar structure in their case work. In addition, electron activated dissociation (EAD) was applied to analyze N-benzyl norheptedrone, which showed only one product ion in the CID mode. The result showed that for compound with limited product ions in the CID mode, the EAD mode can give more complementary information for structure elucidation. In addition, quantitative NMR (qNMR) was applied for the quantification of four powdered/crystal and two herbal blend seized samples. To our knowledge, no analytical data about the compounds 3 and 4 have appeared until now, making this the first report on these compounds.