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Dimethyldithiodenafil and dimethylthiocarbodenafil were detected in three powder products.Dimethyldithiodenafil and dimethylthiocarbodenafil were established using HRMS and NMR.Dimethyldithiodenafil was subjected to an X-ray structural analysis and PDE assay.Three powder products contained 12–19 mg dimethyldithiodenafil per tube.Three powder products contained 1.4–3.9 mg dimethylthiocarbodenafil per tube.Two analogs of sildenafil (compounds 1 and 2) were detected in three powder products acquired from online drug markets during an LC–UV–MS analysis of psychotropic drugs. Their structures were established by high-resolution mass spectrometry and NMR spectroscopy. Compound 1 was identified as 5-(5-(3,5-dimethylpiperazine-1-carbonothioyl)-2-ethoxyphenyl)-1-methyl-3-propyl-1H-pyrazolo[4,3-d]pyrimidine-7(6H)-thione and named dimethyldithiodenafil. Compound 2 was identified as 5-(5-(3,5-dimethylpiperazine-1-carbonothioyl)-2-ethoxyphenyl)-1-methyl-3-propyl-1H-pyrazolo[4,3-d]pyrimidin-7(6H)-one and named dimethylthiocarbodenafil. Compound 1 was subjected to the phosphodiesterase assay (IC50 = 0.20 nM). The three powder products were found to contain 12–19 mg of dimethyldithiodenafil and 1.4–3.9 mg of dimethylthiocarbodenafil per tube.