The optimal conditions of the codeine solutions luminescence were determined: 0.1 N H₂SO₄, λ_ex = 300 нм, l_lum  = 345 нм. The luminescence procedure of it^’s determination (25 - 1000 µg/ml) was developed. The limit of detection of the codeine is 3 µg/ml, the relative standard deviation is not more than 0,05. The procedure for the determination of codeine in samples of drugs “Sedalgin NEO”, “Pentalgin-N”, “Pentalgin Plus” with using thin-layer chromatography and addition method was approbated. According to results of the luminescence determination of the codeine in samples drugs the developed procedure can be recommended for using in practice of expert institutions.