In this article, a simple method for either transfer of silver nanoparticles from formamide to chloroform or to form a film at their interface is demonstrated. The transfer of the particles is a two-step size-dependent process. The size distribution of the colloidal hydrophobic silver particles in chloroform was almost the same as that before its transfer. Particles can be isolated by evaporation of chloroform. During evaporation, the hydrophobic particles become hydrophilic (charged) due to the formation of bilayer of CTAB over their surface. The isolated particles can be re-dispersed easily in polar solvents such as water and methanol. Nanocrystalline film of Ag is also prepared at the formamide-chloroform interface using suitable stabilizers in two immiscible layers. The nanocrystals have been characterized by various microscopic and spectroscopic techniques. The free standing film could be easily transferred on solid support. (C) 2009 Elsevier Inc. All rights reserved.