This paper discusses the effects of 1,1,2,2 tetrachlorethylen (TCE) non-solvent addition on the independent (electrical conductivity, dielectric constant, surface tension and the rheological properties of the solution etc.) and dependent parameters (number of Taylor cones per square meter (NTC/m(2)), spinning performance for one Taylor cone (SP/TC), total spinning performance (SP), fiber properties such as diameter, diameter uniformity, non-fibrous area) in roller electrospinning of polyurethane (PU). The same process parameters (voltage, distance of the electrodes, humidity, etc.) were applied for all solutions during the spinning process. According to the results, the effect of TOE non-solvent concentration on the dielectric constant, surface tension, rheological properties of the solution and also spinning performance was important statistically. Beside these results, TOE non-solvent concentration effects quality of fiber and nano web structure. Generally high fiber density, low non-fibrous percentage and uniform nanofibers were obtained from fiber morphology analyses.