Self-assembled 3D hierarchical Bi2W1−xMoxO6 heterostructures with varying x (x = 0, 0.2, 0.4, 0.6, 0.8 or 1.0) with different morphologies were synthesised via a facile one-pot solvothermal method and their photocatalytic activity towards the oxygen evolution reaction (OER) from water under natural sunlight was tested.