In this work the flower-like hierarchical structures (HS) based on 3D pristine ZnO, ZnO:Eu3þ and ZnO:Eu3þ@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), UVevis and photoluminescence (PL) spectroscopies. The proposed synthesis approaches allow to obtain highly crystalline 3D ZnO, ZnO:Eu3þ and ZnO:Eu3þ@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 pproximately 3 mm. Au nanoparticles (size ~ 10 nm) are successfully deposited on ZnO HS surface. Luminescent studies show that ZnO is an ideal matrix for incorporation of Eu3þ ions in broad concentration range (Eu3þ ¼ 1.0 at%e5.0 at%) with an efficient red luminescence. The strong UV emission in ZnO, as well as ZnO:Eu3þ HS is observed under 325 nm excitation. Doping of ZnO HS matrix by Eu3þ ions leads to the red shift of deep level emission peak (DLE). The PL intensity reaches the maximum up to 5 at% Eu3þ. The photocatalytic properties of ZnO and ZnO:Eu3þ@Au HS were investigated under UVeVis light irradiation towards rhodamine 6G. The obtained results demonstrate the synergetic effect of the deposited gold nanoparticles and Eu3þ doping on photocatalytic activity of ZnO:Eu3þ@Au HS in comparison to pristine ZnO and ZnO:Eu3þ HS.