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Abstract Inorganic particles are effective photocatalysts for the liquid-state production of organic precursors and monomers at ambient conditions. However, poor colloidal stability of inorganic micro- and nanoparticles in low-polarity solvents limits their utilization as heterogeneous catalysts and coating them with surfactants drastically reduces their catalytic activity. Here we show that effective photo-oxidation of liquid cyclohexane (CH) is possible using spiky particles from metal oxides with hierarchical structure combining micro- and nanoscale structural features engineered for enhanced dispersibility in CH. Nanoscale ZnO spikes are assembled radially on α-Fe₂O₃microcube cores to produce complex ‘hedgehog’ particles (HPs). The ‘halo’ of stiff spikes reduces van der Waals attraction, preventing aggregation of the catalytic particles. Photocatalysis in Pickering emulsions formed by HPs with hydrogen peroxide provides a viable pathway to energy-efficient alkane oxidation in the liquid state. Additionally, HPs enable a direct chemical pathway from alkanes to epoxides at ambient conditions, specifically to cyclohexene oxide, indicating that the structure of HPs has a direct effect on the recombination of ion-radicals during the hydrocarbon oxidation. These findings demonstrate the potential of inorganic photocatalysts with complex architecture for ‘green’ catalysis.