In this Letter, we present a portable all-fiber fluorescent detection system based on metal-lined hollow-core fiber (MLHCF) for the ultra-sensitive real-time monitoring of mercury ions (Hg2+). The system employs a rhodamine derivative as the probe. The hollow core of the MLHCF serves as both the flow channel of the liquid sample and the waveguide of the optical path. The metal coating in the intermediate layer between the capillary and the polyimide (PI) coating in the MLHCF provides good light confinement, enhancing the interaction between the sample and the incident light for better fluorescence excitation and collection efficiency. Additionally, further enhancement is achieved by placing an inserted filter along the light path to reflect the excitation light back to the MLHCF. A 3-cm length of MLHCF enables simultaneous excitation of a 40-µL sample volume and collection of most of its fluorescent signal in all directions, thereby significantly contributing to its exceptional sensitivity with a limit of detection (LOD) of 2.3 ng/L. The all-fiber fluorescence-enhanced detection device also shows rapid response time, excellent reusability, and selectivity. This system presents an online, reproducible, and portable solution for the trace detection of Hg2+ and provides a promising way for detecting other heavy metal ions.