This approach provides a new technique to synthesize silver nanoparticles (AgNPs) using CO2-expanded liquids (CXLs) as the processing medium. A soluble form of silver carboxylate, silver isostearate (AgISt), was synthesized and characterized. The XRD and DSC analyses indicated that the methylated branched alky chains in AgISt exhibited a steric hindrance to impede the growth of layered structure of AgISt molecules, which led to the high solubility of AgISt in nonpolar solvents. By using AgISt as silver precursor, AgNPs of 2.64 +/- 0.51 nm in diameter were synthesized in CO2-expanded heptane with H-2 as the reducing agent. The ATR-FTIR analysis showed that the produced AgNPs were capped with isostearic acid, which was derived from the reduction of AgISt. Hence, the isostearic acid capped AgNPs were well-dispersed in heptane to form a stable silver organosol.