This paper describes a new method to prepare organic-soluble silver nanoclusters (AgNCs) protected by thiophenol (TP) (1), 4-fluorothiophenol (4-FTP) (2) and 4-methylthiophenol (4-MeTP) (3) ligands. Those ligands was chosen to investigate the effect of the substituting group attached to the thiophenol moiety from the point of withdrawing group (fluorine atom) and donating group (methyl group) and their effect in the stability of silver clusters. The optical properties of the as synthesized silver nanoclusters exhibited a broad surface plasmon resonance (SPR) peaks at 464 nm, 474 nm and 475 nm for Ag@SPhX (X= H, F, and Me), respectively. All the three types of silver nanoclusters (1-3) are highly stable even when being exposed to air as indicated by their absorption spectra. There is almost no change in the intensity of their UV-vis absorption peaks even after 24 hours of air exposure. Therefore, we succeeded in the separation of highly stable silver nanoclusters versus the ambient oxidative condition. The morphology and particles size of the as synthesized nanoclusters were estimated by using transmission electron microscopy (TEM). It was found that, all the three types of silver clusters have a homogenous particle size distribution, with an average particle size of about 2 nm. The average chemical formula and the silver to ligand (Ag/L) ratio were calculated by thermogravimetric analysis (TGA) of the synthesized silver nanoclusters.