Within the manufacturing industry, production velocity plays a key role with respect to economic turnover rates. This issue is often a pivotal factor in the incorporation of developing technologies. For electrostatic spinning, which is based on the formation of nanoscopic fibrous elements and relatively low fiber throughput values, an increase is highly desirable for application at both laboratory and industrial scales. In this paper, a joint experimental–theoretical study is conducted to explore the impact of the solution properties on improving the electrospinning throughput. The needleless electrospinning process was selected because of its increased production rate and higher upscaling potential than other electrospinning approaches. Polyurethane solutions using polysiloxane additives were used as spinning solutions. The results show that additives, such as PDMS-OH, that decrease the solution surface tension and increase the solution viscosity can significantly improve the production rate of nanofibrous scaffolds. Our experiment shows that with as low as 2% w/w additive, the throughput increased from 0.99 to 5.55 56 g/cm². The reasons are investigated by theoretical analyses. As such, the use of additives is beneficial for high throughput because surface tension, viscosity, and relative permittivity can be tailored to increase the electrospinning throughput. This study provides a stepping stone toward higher electrospinning throughput by tailoring solution properties with additives.