Dewetting induced self-organisation was used to prepare an ordered microstructure from a highly volatile liquid. Dewetting of an evaporating iron oxide precursor solute on silicon substrate resulted in arrays of microdots with nearly hexagonal and tetragonal symmetries. Ordered structures form either by stick-slip motion or fingering instability at the receding contact line of evaporating droplets. Subsequent thermal treatment at 550 °C yields crystalline Fe(2)O(3) microdots with a diameter range of 1-4 μm. The size, density and shape of the microdots can be changed by using patterned substrates with different surface energies.