More than 46 phosphodiesterase type 5 (PDE5) inhibitor analogues have been found to be present as illegal adulterants in various forms of health food products (powder, tablet, capsule, etc.), thereby placing the health of consumers at risk through product intake. In this study, 164 samples advertised to be effective at enhancing male sexual performance were collected over a 4-year period (2009–2012) from the Korean on-line or off-line market and screened. An LC-MS/MS method was employed to screen for the presence of 48 compounds including sildenafil, tadalafil, vardenafil and their analogues. Method validation established LOQs (0.30–10.00 ng ml−1 or ng g−1) and recoveries (spiked in liquid sample, 84–112%; spiked in solid sample, 83–110%). Most of the illicit products screened were adulterated with 14 of the PDE5 derivatives under examination, including considerable amounts of sildenafil and tadalafil; of the 48 compounds, tadalafil was the most frequent adulterant (42.6%), followed by sildenafil (27.9%). Specifically, tadalafil concentration ranges (mg g−1) in the samples collected over the 4-year period were determined as follows: 2.91–52.20 (2009), 4.50–108.10 (2010), 0.37–101.40 (2011), and 0.08–138.69 mg g−1 (2012). The concentration ranges (mg g−1) of sildenafil were also at high levels: 4.90–117.96 (2009), 1.30–369.93 (2010), 0.03–241.77 (2011), and 18.34–297.91 mg g−1 (2012). The results of screening for PDE5 inhibitor pharmaceuticals as adulterants in illicit health food products are of great significance with respect to the protection of public health and consumer safety.