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The heterostructure EuSe/Ag nanoparticles (NPs) were prepared through one-step colloid chemical method. Blue fluorescent EuSe NPs were prepared by amine reducing method with oleylamine (OLA) as surface stabilizer. The colloid microemulsion was formed through the mixture of AgNO3 aqueous solution and the EuSe n-Hexane solution. On the interface, Ag+ ions could be reduced to Ag NPs by OLA. Finally heterogeneous EuSe/Ag NPs were obtained. The structure and properties of EuSe NPs and EuSe/Ag NPs were characterized by photoluminescence (PL), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results showed that the luminescence resonance energy transfer (LRET) occurred on the interface of EuSe NPs and Ag NPs. Also it demonstrated that the linear enhanced LRET effect happened with increasing the concentration of Ag+. All these properties make our heterostructural EuSe/Ag NPs to have interesting potential applications for ions detection and biosensors.