For the recovery of Ag(I) from the leachate of silicon solar cells, a nitrate solution containing Ag(I) and Al(III) was subjected to solvent extraction with trioctylphosphine oxide (TOPO). TOPO selectively extracted Ag(I) over Al(III) at low nitric acid concentrations. Most of the Ag(I), along with small amount of Al(III), was extracted from the 10 mol/m(3) nitric acid solution using 500 mol/m(3) TOPO. HNO3 stripped both Ag(I) and Al(III) from the metal-loaded TOPO, whereas thiourea could selectively strip Ag(I) from the loaded TOPO. Metal-loaded TOPO could be regenerated after stripping of Ag(I) with thiourea, followed by stripping of Al(III) with HNO3. A process flow sheet for Ag(I) recovery from the nitrate leachate of silicon solar cells was proposed.