A substoichiometic analytical method of high sensitivity combined with adsorptive sampling has been worked out for the determination of traces of silver in palladium making use of the selective deposition of microquantities of silver from aqueous solutions of palladium salts on cathodically polarized platioum surfaces. The stability and reporducibility of the saturation values of deposited silver are practially independent of the content and concentration of silver and palladium in the solution. The sensitivity proved to be 0.01 ppm, the accuracy ± 30 per cent.