The effects of various parameters on the photoassisted reduction of silver ions to metallic deposits on powder titanium dioxide has been studied. The initial deposition rate (i) varied with the starting concentration of Ag + ions according to a Langmuir-Hinshelwood mechanism, (ii) was almost independent of the temperature around 300 K, and (iii) was proportional to the radiant flux (300 nm < λ < 400 nm) of photons absorbable by TiO 2, at least up to a value of 7.6 × 10 15 photons s −1 cm −2. For the same illumination conditions, an apparent initial quantum yield of 0.16 was calculated at room temperature in the case of complete coverage of the surface by Ag + ions. Transmission electron microscopy revealed that silver initially formed particles between 3 and 8 nm in diameter. For larger amounts of silver deposited and longer illumination times, large crystallites (up to 400 nm) were also observed. This prevented the photosensitive surface from being substantially covered and, for instance, a silver-to-titania mass ratio of ca. 2.4 was reached without a decrease in the deposition rate. This phenomenon, as well as the removal of silver ions down to the detection limit, supports the possible use of this method for the recovery of silver from dilute aqueous solutions. In this connection, preliminary experiments showed that silver was selectively extracted from equimolar solutions of Ag + and Cu 2+ ions (cf. electrolytic baths) and that it was also recovered in the presence of thiosulfate ions (cf. photographic fixing baths).