An easily available, simultaneous identification/determination procedure for phentolamine (PHE) and sildenafil (SIL) in adulterated dietary supplements was established by using a combination of three different analytical methods; thin-layer chromatography (TLC), liquid chromatography-mass spectrometry (LC/MS) and a high-performance liquid chromatography (HPLC)/photo-diode-array. The sample solution for TLC was applied to silica gel 60 F(254) plates with chloroform/ammonia solution (28)/methanol (70:5:3, lower layer) and chloroform/diethylamine/methanol (15:3:2) as the developing solvent. Spots were located under UV radiation at 254 nm. Mass spectra of PHE and SIL by LC/MS were investigated with electrospray ionization (ESI) interface, under both positive and negative ion mode. The HPLC analysis was performed on a column of Wakosil 5C18 (4.6 mm x 150 mm, 5 microm) with water/methanol/acetonitrile/triethylamine (580:250:170:1) adjusted with phosphoric acid to pH 3.0 as the mobile phase, and the effluent was monitored with a photo-diode-array detector. Quantitative HPLC analysis of PHE and SIL were detected at 280 nm. When this procedure was applied to commercial soft drinks, PHE and SIL were identified and determined at a concentration of 17 mg PHE and 44 mg SIL per bottle, respectively. The procedure described here is available for the screening of PHE and SIL in adulterated supplements.