Plasma and saliva pharmacokinetics of dipyrone (CAS 5907-38-0) metabolites, 4-methylaminoantipyrine (MAA), 4-aminoantipyrine (AA), 4-formylaminoantipyrine (FAA) and 4-acetylaminoantipyrine (AAA), has been studied in 10 healthy volunteers, after oral administration of 1.0 g dipyrone, MAA, AA, FAA and AAA saliva concentrations correlated significantly with the respective plasma concentrations (r = 0.81, r = 0.62, r = 0.83 and r = 0.91, p < 0.001). MAA and AA concentrations in saliva were lower than in plasma while the FAA and AAA saliva concentrations were similar to the respective plasma concentrations. The saliva/plasma concentration ratios were highly dependent on sampling time. The elimination half-life of the final metabolites FAA and AAA can be equally evaluated from plasma and saliva data. For MAA, plasma and saliva t1/2 values were significantly correlated despite a substantial intra-subject difference. No correlation was found for AA plasma and saliva derived pharmacokinetic parameters. Similar to the plasma AAA/AA ratio, the saliva AAA/AA ratio in spot sample 6 h following oral dose might be proven to be a reliable discriminatory index for acetylation phenotyping.