An accurate, rapid, and sensitive GLC determination of alprenolol and oxprenolol in serum is described. This method combines an electron-capture detector with a wall-coated open tubular column. The lowest detectable amount of the halogenated (heptafluoroacyl) derivatives of alprenolol and oxprenolol is 2 pg. The high resolving power and the rapid elution time of the wall-coated open tubular column dramatically improve the performance (accuracy and sensitivity) of the conventional electron-capture detector and packed column system in these determinations. This method allows the use of small volumes of sample (100-200 microliter), does not require redistilled reagents, and has a simplified extraction procedure.