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The breath figure technique is one of the most promising strategies for the fabrication of large-sized patterns containing an ordered two-dimensional array of holes. In this review, particular emphasis is placed on the static breath figure technique, which is a robust methodology suitable for various polymers including linear polystyrene (PS), amphiphilic diblock copolymers and polymer/inorganic precursor hybrid films. The resultant highly ordered microporous polymer films can be used asa mask for lithography. Moreover, the microporous polymer films can be surface modified and cross-linked by UV irradiation. The surface modified films can potentially be applied as a cell scaffold and the cross-linked polymer/hybrid films can be used as templates for the growth of nanomaterial arrays