In this study, bimetallic platinum/gold nanoparticles (Pt/Au NPs) were found to exhibit peroxidase-like activity, and the deposition of mercury was found to switch the enzymatic activity to a catalase-like activity. Based on this phenomenon, we developed a new method for detecting mercury ions through their deposition on bimetallic Pt/Au NPs to switch the catalytic activity of Pt/Au NPs. Pt/Au NPs could be easily prepared through reduction of Au 3+ and Pt4+ by sodium citrate in a one-pot synthesis. The peroxidase catalytic activity of the Pt/Au NPs was controlled by varying the ratios of Pt to Au. The Pt0.1/Au NPs (prepared with a [Au 3+]/[Pt4+] molar ratio of 9.0/1.0) showed excellent oxidation catalysis for H2O2-mediated oxidation of Amplex? Red (AR) to resorufin. The oxidized product of AR, resorufin, fluoresces more strongly (excitation/emission wavelength maxima ca. 570/585 nm) than AR alone. The peroxidase catalytic activity of Pt0.1/Au NPs was switched to catalase-like activity in the presence of mercury ions in a 5.0 mM tris(hydroxymethyl)aminomethane (Tris)-borate solution (pH 7.0) through the deposition of Hg on the particle surfaces owing to the strong Hg-Au metallic bond. The catalytic activity of Hg-Pt0.1/Au NPs is superior (by at least 5-fold) to that of natural catalase (from bovine liver). Under optimal solution conditions [5.0 mM Tris-borate (pH 7.0), H2O2 (50 mM), and AR (10 μM)] and in the presence of the masking agents polyacrylic acid and tellurium nanowires, the Pt0.1/Au NPs allowed the selective detection of inorganic mercury (Hg2+) and methylmercury ions (MeHg+) at concentrations as low as several nanomolar. This simple, fast, and cost-effective system enabled selective determination of the spiked concentrations of Hg2+ and MeHg+ in tap, pond, and stream waters. This journal is ? 2012 The Royal Society of Chemistry.