The bivariate calibration algorithm was applied to the spectrophotometric simultaneous determination of trimethoprim (TMP), sulfamethoxazole (SMX) or sulphamethoxypyridazine (SMP) binary mixtures in pharmaceutical and veterinary products. The results obtained were compared with those from derivative spectrophotometry. The statistical evaluation of the method bias showed that the proposed procedure is comparable with commonly used first-derivative spectrophotometry. However, the advantage of bivariate calibration is its simplicity, due to the minimal spectra manipulation when compared with derivative techniques.