A modification of the polyol method has been shown to result in improved efficiency and enhanced kinetics for the synthesis of silver nanocrystals when compared with the traditional polyol method. The Ag nanocrystals produced were characterized using Xray diffraction and transmission electron microscopy. Accordingly, the exhibited Ag crystal structure, corresponding lattice constants, and resultant particle sizes were determined by these means. In addition, using Fourier transform infrared spectroscopy, it was found that a solid-state reaction between the AgNO3 and the Poly (vinylpyrrolidone) (PVP) takes place prior to their dissolution in ethylene glycol. Moreover, when crystals grow under total rest conditions, they do not develop a spherical morphology as in the traditional polyol method, but a well-defined geometric shape showing preferential crystallographic growth directions. Under the experimental conditions of this work, the exhibited nanocrystal shapes were quasi-planar hexagonal. Apparently, PVP interacts with the FCC crystal structure promoting growth on the {100} preferential direction by playing the role of an atomic arranger. (C) 2007 Wiley Periodicals, Inc.