Co3O4 multilayered structures were successfully synthesized by a facile poly (ethylene glycol 20000) (PEG-20000) assisted hydrothermal technique in combination with calcination method. The final Co3O4 multilayered structures inherited perfectly the morphology of the preliminarily hydrothermal products. Experimental results obtained from the different growth stages demonstrate that the as-prepared precursor exhibit an interesting time-dependent evolution of building blocks, from urchin to multilayer. The possible formation mechanism for the hierarchical structures with various architectures is presented on account of the self-assembled growth induced by Ostwald ripening. Because of the unique structured composed of slices, the photocatalytic activity of the products was examined by measuring the photodecolourisation of methyl violet solution with ultraviolet radiation. The result shows that our products have a good photocatalytic activity. (c) 2015 Elsevier B.V. All rights reserved.