Injectable solutions used in treatment of intense pain are based on combinations of active ingredients such as metamizole sodium (MTZ), pitofenone hydrochloride (PTF) and fenpiverine bromide (FPB). The simultaneous chromatographic assay of such combinations poses difficulties due to their structural variety, highly polar character, and wide concentration ranges (500 mg mL-1 for MTZ, 2 mg mL-1 for PTF and 0.02 mg mL-1 for FPB). Fast hydrolysis of MTZ on aqueous dilution causes additional problems due to impurity (MTC) formation. Sodium hexane sulphonate (10 mM) was used as ion pairing agent for PTF, FPB and MTC in a mobile phase consisting of 48/52 (v/v) methanol and aqueous 0.2% triethylamine at pH=3. The ionic liquid 1-butyl-1-methyl-pyrrolidinium tetrafluoroborate (10 mM) was used as mobile phase additive to preserve the MTZ peak symmetry. The minor active ingredient FPB was selectively extracted into 1-octanol by ion pair formation with picric acid. A 20 μL aliquot of the organic layer was directly injected into the column.