Abstract A sensitive and selective spectrophotometric method for silver has been established by reacting silver(I) with 2-(3,5-dibromo-2-pyridylazo)-5-diethylaminophenol (3,5-diBr-PADAP) in the presence of an anionic surfactant, sodium lauryl sulphate. The molar absorptivity is 7.7 × 10 4 l.mole −1.cm −1 at 570nm. The molar ratio of silver to 3,5-diBr-PADAP is 1:2. Beer's law is obeyed from 0.1 to 1 ppm of silver. With EDTA as masking agent, common ions do not interfere. The method has been applied to the determination of silver in waste water.