A facile and novel way was reported here for the synthesis of hydrophobic Ag nanoparticles (NPs), using AgNO₃, tri-n-octylphosphine (TOP) and sulfur (S) powder in process. TOP was used as solvent, reducing agent and stabilizer. S could chelate with excessive TOP to form trioctylphosphine sulfide (TOPS), which served as second capping agent. The hydrophobic Ag NPs could be transformed into hydrophilic state through ligand exchange. Furthermore, surface-enhanced Raman scattering (SERS) spectra of 4-aminothiophenol (4-ATP) were obtained on the hydrophobic and hydrophilic Ag NPs modified substrates, indicating that the as-synthesized Ag NPs had great potential for high sensitive optical detection applications.