Mesoporous SiO2/Zn2SiO4:Eu3 hollow nanospheres were successfully synthesised via the combination of layer-by-layer and combustion technique. The structures and morphologies of as-obtained SiO2/Zn2SiO4:Eu3 nanospheres were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and N2 adsorption-desorption isotherms techniques. SiO2/Zn2SiO4:Eu3 nanospheres can be tested as adsorbents to remove heavy metal ions, which showed good adsorption capacity and selectively adsorption especially for Pb2 and Cu2 than Cd2 . The optical properties studies of as-synthesised samples showed that mesoporous SiO2/Zn2SiO4:Eu3 hollow nanospheres had strong red emission around 618 nm, and the optimal loading dosage of Eu3 was determined. Moreover, the mesoporous SiO2/Zn2SiO4:Eu3 hollow nanospheres could offer cell optical imaging by conventional fluorescence with 543 nm excitation.