Monodispersed rhodium nanoparticles were synthesized through a flexible and very simple approach in a monosurfactant system by thermolysis of RhCl3, in which oleyl amine serves as capping, reducing agent, and high boiled solvent. The coated rhodium nanoparticles are monodispersed with 4 nm diameter and well characterised by TEM microscopy, UV-Vis spectroscopy, and X-ray diffraction measurements. The as prepared rhodium nanoparticles have the tendency to aggregate forming well-organized large symmetrical and spherical 3-D superstructures which generally have diameters between 40-60 nm as revealed by the characteristic TEM images. Due to the organic monolayer that encloses the nanoparticles are soluble in non-polar organic solvents.