Segmented polyurethane (SPU) nanofiber mats were prepared by electrospinning technique using the combination of four different solvents viz. tetrahydrofuran, N,N′‐dimethyl formamide, N,N′‐dimethyl acetamide, and dimethyl sulfoxide. Morphology of the electrospun nanofibers was examined by field emission scanning electron microscope. Experimental results revealed that the morphologies of polyurethane nanofiber mats have been changed significantly with the solvent selection for the electrospinning. It was observed that the diameters and morphology of the SPU nanofibers were influenced greatly by the use of combination of solvents. The uniform polyurethane nanofibers without beads or curls could be prepared by electrospinning through the selection of combination of good conductive and good volatile solvent viz. 7.5 wt/v% of SPU in N,N′‐dimethyl formamide/tetrahydrofuran (30 : 70 v/v) solutions at 20 kV applied voltages and volume flow rate of 1 ml/min. On the basis of the results obtained from this investigation, it has been established that solvent selection is one of the driving factors for controlling the morphology of the polyurethane electrospun nanofiber mats. The well‐controlled morphology of electrospun polyurethane nanofiber mats could be useful for many potential industrial applications such as in biomedical, smart textiles, nanofiltration, and sensors. Copyright © 2013 John Wiley & Sons, Ltd.