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In this work the flower-like hierarchical structures (HS) based on 3D pristine ZnO,ZnO∶Eu3+ and ZnO∶Eu3+@Au were successfully obtained by a template-free solvothermal and deposition-precipitation method.The decolorization/photodegradation of these structures towards model organic dye (rhodamine 6G) was studied.The synthesized ZnO-based HS were characterized by X-ray diffraction (XRD),scanning electron microscopy (SEM),UV-vis and photoluminescence (PL) spectroscopies.The proposed synthesis approaches allow to obtain highly crystalline 3D ZnO,ZnO∶Eu3+ and ZnO∶Eu3+@Au composites.Results of scanning microscopy show that ZnO flower-like HS are assemblies from smaller components,forming larger ones,the whole ZnO structure was approximately 3 μm.Au nanopartides (size ～ 10 nm) are successfully deposited on ZnO HS surface.Luminescent studies show that ZnO is an ideal matrix for incorporation of Eu3+ ions in broad concentration range (Eu3+ =1.0 at％-5.0 at％) with an efficient red luminescence.The strong UV emission in ZnO,as well as ZnO∶Eu3+ HS is observed under 325 nm excitation.Doping of ZnO HS matrix by Eu3+ ions leads to the red shift of deep level emission peak (DLE).The PL intensity reaches the maximum up to 5 at％ Eu3+.The photocatalytic properties of ZnO and ZnO∶Eu3+@Au HS were investigated under UV-Vis light irradiation towards rhodamine 6G.The obtained results demonstrate the synergetic effect of the deposited gold nanoparticles and Eu3+ doping on photocatalytic activity of ZnO∶Eu3+@Au HS in comparison to pristine ZnO and ZnO∶Eu3+ HS.