TLC analysis of extracts of Pilosocereus maxonii (Rose) Byles and Rowley detected six identifiable alkaloids. Preparative TLC aided in the crystallization of the hydrochlorides of N-methyl-3,4-dimethoxyphenethylamine, N-methyl-3-methoxytyramine, and N,N-dimethyl-3-methoxytyramine. Traces of 3,4-dimethoxyphenethylamine (TLC and mass spectrometry), tyramine (TLC), and N-methyltyramine (TLC) were identified. While all of these compounds were isolated and/or detected previously in other cactus species, this study is the first reported crystallization of N-methyl- and N,N-dimethyl-3-methoxytyramine from a natural source.