Self-assemblies of nanoparticles of CeO2/ZnTi layered double hydroxides (CeO2/ZnTi-LDH) and the derived CeO2/Zn2TiO4 systems are reported as novel efficient nano-photocatalysts for phenol degradation. The spontaneous formation and organization of nanoparticles of CeO2 on ZnTi-LDH matrix is based on a cheap, nontoxic and facile technique that invokes the manifestation of the structural memory effect of LDH in aqueous solution of Ce(SO4)(2). It was found that the composition of the brucite-type layer has a major effect on establishing the performances of the phenol photodegradation process. Moreover the LDH layered matrix offers multiple advantages, such as manipulation of the brucite-like layer composition and the insertion of key cations, like Zn2+ and Ti4+, but also the possibility to supply a good dispersion of the metal cations within the layers, which may act as charge separation centers enhancing the efficiency in subsequent applications. These results open new opportunities in the development of hybrid nano-assemblies systems able to utilize their collective properties for facilitating cumulative photocatalytic properties for "green" removal of dangerous pollutants. (C) 2013 Elsevier B.V. All rights reserved.