A highly sensitive label-free chemical sensing platform for the detection of various metal ions is demonstrated. The chemical sensor was derived from a single-mode fiber that is inserted into the ceramic tube with epoxy resin (ER) on the end face for reflecting light and forms the Fabry-Perot (F-P) interferometric cavity. Multilayer chitosan (CS)/polyacrylic acid (PAA) were coated on the surface of the epoxy resin and act as the sensitive film. Based on the analysis of the sensing principle and the F-P cavity structure, the parameters were numerically simulated and experimentally evaluated, which enables ease of fabrication and real-time modulation of the cavity length. The sensitivity of sensing Ni2+, Zn2+, and Na+ reached 9.95 x 10(-4) nm ppb(-1), 2.31 x 10(-4) nm ppb(-1), and 4 x 10(-4) nm ppb(-1), respectively, and the sensing results were theoretically analyzed by the Langmuir adsorption model, which corresponds to the surface atom percentage results obtained by SEM and EDS measurements for sensing three types of metal ions. The proposed ER/CS/PAA multilayer film-coated F-P sensor can be employed as a probe, which features label-free, highly sensitivity, real-time monitoring, ease of measurement, stability, and therefore provides a remarkable analytical platform for chemical applications.