Surface-enhanced Raman Scattering (SERS) fiber probe provides abundant interaction area between light and materials, permits detection within limited space and is especially useful for remote or in situ detection. A silver decorated SERS fiber optic probe was prepared by hydrothermal method. This method manages to accomplish the growth of silver nanoparticles and its adherence on fiber optic tip within one step, simplifying the synthetic procedure. The effects of reaction time on phase composition, surface plasmon resonance property and morphology were investigated by X-ray diffraction analysis (XRD), ultraviolet-visible absorption spectrum (UV-VIS absorption spectrum) and scanning electron microscope (SEM). The results showed that when reaction time is prolonged from 4–8 hours at 180 °C, crystals size and size distribution of silver nanoparticles increase. Furthermore, the morphology, crystal size and distribution density of silver nanoparticles evolve along with reaction time. A growth mechanism based on two factors, equilibrium between nucleation and growth, and the existence of PVP, is hypothesized. The SERS fiber probe can detect rhodamin 6G (R6G) at the concentration of 10−6 M. This SERS fiber probe exhibits promising potential in organic dye and pesticide residue detection.