A pyrene-based derivative, 2-((pyrene-1-ylmethylene)amino)ethanol (PE) nanoparticle, was encapsulated via water-in-oil-in-water (W/O/W) double emulsion with the solvent evaporation method by one-pot reaction and utilized as a fluorescence turn-on sensor for detecting Fe3+, Cr3+, and Al3+ ions. Magnetic nanoparticles (MNPs) embedded in polycaprolactone (PCL) were used as the magnetic-sensitive polyelectrolyte microcapsule-triggered elements in the construction of the polymer matrix. The microcapsules were characterized by ultraviolet–visible (UV–Vis) and photoluminescence (PL) titrations, quantum yield (Φf) calculations, 1H nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and superconducting quantum interference device magnetometry (SQUID) studies. This novel responsive release of the microcapsule fluorescence of the turn-on sensor for detecting trivalent cations was due to the compound PE and the MNPs being incorporated well within the whole system, and an effective thermal and kinetic energy transfer between the core and shell structure efficiently occurred in the externally oscillating magnetic field. The magnetic-sensitive fluorescence turn-on microcapsules show potential for effective metal ion sensing in environmental monitoring and even biomedical applications. Under the optimal controlled-release probe fluorescence conditions with high-frequency magnetic field treatment, the limit of detection (LOD) reached 1.574–2.860 μM and recoveries ranged from 94.7–99.4% for those metals in tap water.