A new method for direct patterning of Poly(dimethylsiloxane) (PDMS) microstructures is developed by taking advantage of photorefractive effect in a functionalized substrate. Here we show that when a x-cut Iron doped Lithium Niobate (LN) crystal is exposed to appropriate structured laser light, a charge density pattern builds-up in the crystal and a space charge field arise that is able to induce self-patterning of the PDMS liquid film deposited on its surface via the dielectrophoretic effects. Proper heating treatment allows to achieve polymeric linking process creating a solid and stable PDMS microstructures. The self-patterned structures replicate the illuminating light pattern. We show that 1D and 2D patterning of PDMS gratings can be achieved. This new soft-lithographic approach can pave the way for realizing PDMS micro-structures with high degree of flexibility that avoids the need of moulds fabrication.