A Rhodamine-based fiber-optic sensor has been developed to detect mercury ions in aqueous environments. The fiber-optic sensor was composed of a mercury-sensing thin film, plastic optical fibers, and a spectrometer. The mercury-sensing thin film with the synthesized Rhodamine derivatives was fabricated with Sol-Gel process. A light emitted by a light source is guided by plastic optical fibers into the thin film in an aqueous solution and a reflected light is analyzed with the spectrometer. The experiment exhibits that an absorbance in the thin film is increased as mercury concentration is increased in the solution and the absorbance by mercury is higher than that by other heavy metals. The fiber-optic sensor exhibits high chromogenic phenomenon of mercury ions among various heavy metals and the correlation between absorbance and mercury concentration in the aqueous environments.