We develop a highly effective silole-infiltrated photonic crystal (PC) film fluorescence sensor with high sensitivity, good selectivity and excellent reproducibility for Fe3+ and Hg2+ ions. Hexaphenylsilole (HPS) infiltrated PCs show amplified fluorescence due to the slow photon effect of PC because the emission wavelength of HPS is at the blue band edge of the selected PC’s stopband. The fluorescence can be quenched significantly by Fe3+/Hg2+ ions owing to electron transfer between HPS and metal ions. The amplified fluorescence enhances the sensitivity of detection, with a detection limit of 5 nM for Fe3+/Hg2+ ions. The sensor is negligibly responsive to other metal ions and can easily be reproduced by rinsing with pure water due to the special surface wettability of PC. As a result, a highly effective Fe3+/Hg2+ ions sensor based on HPS-infiltrated PC film has been achieved, which will be important for effective and practical detection of heavy metal ions.