We report the preparation of poly(vinylpyrrolidone) (PVP)-protected Rh nanoparticles by modified polyol method with the reduction of RhCl3 in ethylene glycol at 160 degrees C using AgNO3. This method is used to synthesize highly cubic and octahedral Rh nanoparticles with their well-controlled size similar to 7-14 nm characterized by transmission electron microscopy (TEM). At a low AgNO3 concentration, the appearance of the sharply good morphology of Rh nanoparticles due to their controlled growth of {1 0 0} and {1 1 1} selective surfaces for similar to 10-15 min is observed. Their morphology between cubic and octahedral shape exhibits their competitive growth along the [1 1 1] and [1 0 0] directions. Interestingly, sharply and highly branched Rh nanoparticles with their shapes of very sharp corners or sharp-tip arms growing in the [1 1 1] directions are synthesized for similar to 30 min at the same concentration of RhCl3 and AgNO3 precursors. However, at a higher concentration of AgNO3, the assemblies of Rh multipods leading to large porous Rh nanoparticles are observed. The problems of reaction time and temperature are discussed to clarify the nucleation and growth of Rh nanoparticles. In addition, monolayers of Rh nanoparticles on SERS substrates using a probe as malachite green (MG) molecule exhibit the high sensitivity for their potential applications in chemical and biochemical sensing. (C) 2011 Elsevier B.V. All rights reserved.