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A porous coating assembled with hierarchical 3D Co 3 O 4 urchin-like particles was synthesized by Pulsed Laser Deposition (PLD) and thermal oxidation. Laser ablation of Co B powder, used as the target material, in oxygen atmosphere formed core–shell particles on the coating surface with mainly a metallic Co core and a mixture of Co, B and O accommodating the shell. The thermal oxidation of these core–shell particles in air at 600 °C induces the morphological transformation to urchin-like particles consisting of nanowires (NWs) (diameter: 30–60 nm and length 1–3 μm) grown radially from the core surface. The extrusion marks on the surface of NWs indicate that the stress induced growth process is caused by difference in the thermal expansion coefficient. XRD, Raman, EXAFS and HRTEM analysis confirmed that the NWs are polycrystalline consisting of pure Co 3 O 4 phase. A wet-chemistry hydrothermal procedure was also employed to synthesize nanostructured urchin-like particles which are hollow and the structure is held together by the radially oriented nanorods (diameter: 40–150 nm). During photocatalysis, urchin-like particles synthesized by PLD displayed significantly higher (∼5 times) degradation rates when compared to chemical urchins for degradation of methylene blue dye via a photo-Fenton reaction in presence of H 2 O 2 and visible light. This is mainly attributed to poor stability of the nanorods in the chemical urchin structure. Features such as high surface area, enhanced stability against agglomeration, polycrystalline nature of the NWs, porous surface and superior adhesion, are responsible for the enhanced photocatalytic activity of Co 3 O 4 urchin-like particles assembled in a porous coating synthesized by PLD and thermal oxidation. Reusability tests also demonstrate the robust nature of the catalyst coating. [ABSTRACT FROM AUTHOR]