A new method is devised for the rapid solvent extraction of silver with diluted tributyl phosphate. Thus 40% TBP in butanol quantitatively extracts silver (49.8μg) from 1M nitric acid that is 2M in lithium nitrate as salting-out agent. Silver is stripped with dilute ammonia and is determined photometrically at 495 ran as its red-violet complex withp-diethylaminobenzylidenerhodanine. The effect of acidity, varying TBP concentration and salting-out agent was studied. The probable composition of the extractable species is thought to be AgNO3·(TBP)3 or HAg(NO3)2(TBP)3. Silver can be extracted in presence of a large number of elements with which it is associated in alloys, minerals or fission products. The method is simple, selective and rapid and needs only 30 minutes for the separation and determination.