To investigate the trend of non-controlled drugs of abuse, simultaneous analytical methods were developed using GC–MS and LC–ESI-MS for 8 tryptamines/ beta-carbolines, 6 phenethylamines of typically non-controlled substances in Japan, and, additionally, five legally controlled tryptamines and phenethylamines originally found in fungi or plants. Moreover, the proposed methods were applied to analyses of these drugs in 99 kinds of products (a total number of 123 products purchased at adult shops or via the Internet over the past 2 years in Japan), which potentially advertised psychotropic/psychoactive effects. The samples were extracted with methanol under ultrasonication. After centrifugation, the extracts were filtered prior to injections. GC–MS analysis was performed using a DB-5MS capillary column. Regarding the LC–ESI-MS analysis; the separation of the target drugs was optimized on an ODS column in acetonitrile/MeOH (7:3)–10 mM ammonium formate buffer (pH 3.5)/acetonitrile (95:5) by a linear gradient program and a quantitative analysis was carried out by the monitoring of each [M + H]+ in the positive ion mode of ESI-MS. As a result of the analyses using GC–MS and LC–ESI-MS, 5-MeO-DIPT (the synthetic substance known by the street name “Foxy”) was found in 8 out of the 99 kinds of products. Additionally, AMT (from brown powder), DMT (from dried plant), harmine and harmaline (from dried plant) were also found in some of the 99 products. These analytical methods could be useful for the investigation of the distribution of the non-controlled psychotropic tryptamines/ beta-carbolines and phenethylamines in the market.