We describe a novel method for creating luminescent lanthanide-containing nanoparticles in which the lanthanide cations are sensitized by the semiconductor nanoparticle's electronic excitation. In contrast to previous strategies, this new approach creates such materials by addition of external salt to a solution of fully formed nanoparticles. We demonstrate this postsynthetic modification for the lanthanide luminescence sensitization of two visible emitting lanthanides (Ln), Tb3+ and Eu3+ ions, through ZnS nanoparticles in which the cations were added postsynthetically as external Ln(NO3)3·xH2O salt to solutions of ZnS nanoparticles. The postsynthetically treated ZnS nanoparticle systems display Tb3+ and Eu3+ luminescence intensities that are comparable to those of doped Zn(Ln)S nanoparticles, which we reported previously (J. Phys. Chem. A, 2011, 115, 4031-4041). A comparison with the synthetically doped systems is used to contrast the spatial distribution of the lanthanide ions, bulk versus surface localized. The postsynthetic strategy described in this work is fundamentally different from the synthetic incorporation (doping) approach and offers a rapid and less synthetically demanding protocol for Tb3+:ZnS and Eu3+:ZnS luminophores, thereby facilitating their use in a broad range of applications. © 2013 American Chemical Society.