Nylon 6 nanofibre membranes were prepared by electrospinning of nylon 6 solutions with various volume ratios of trifluoroethyl alcohol (TFE) and formic acid (FA). The effect of the solvent type on the morphology of nylon 6 nanofibre membranes was investigated. Results showed that all membranes studied showed uniform, defect-free structures with very thin nanofibre diameters. The addition of formic acid led to a significant decrease in average fibre diameters. The average fibre diameters were 660, 186, 87, 62 and 30 nm for nylon 6 nonofibre prepared using the binary solution system and trifluoroethyl alcohol/formic acid (100:0), (75:25), (50:50), (25:75) & (0:100) respectively. In addition, the nylon 6 nanofibre membranes prepared using formic acid showed the highest strength with the highest porosity and the lowest average fibre diameters.