Polysulfone membranes having highly ordered pores in uniform micron size range were fabricated using breath figure (BF) templating in combination with phase separation. Specifically, membranes with average pore opening of 1.5µm, 2.5µm, 2.8µm and 3.4µm and tubular pore cross-sections were prepared. Different solvent systems, dilutions and casting conditions were tested to realize BF templating for fabrication of microporous membranes with controlled and uniform pore sizes. PSF dissolved in a solvent-nonsolvent pair of dichloromethane and tertiary amyl alcohol at 6–10% (w/v) concentration cast at 85–95% relative humidity and 30°C resulted in microporous membranes with uniform monodispersed, nearly hexagonally packed pore openings. The cross-sections revealed tubular channels or macrovoids followed by closed or interconnected cellular structure formed due to phase separation. In absence of internal nonsolvent BF templating could occur only in very dilute solution. The work also underscores need for immiscibility of casting solvents with water.