The electrospray process produces micro/nanodroplets for various applications such as thin and uniform coatings, drug carriers and mass spectrometry. In this paper, we study the spray processes of viscoelastic jets using simulations and experiments. In discretized modeling, the jet is perturbed with axisymmetric instability and the growth of this instability causes the jet to break into droplets. For the experiments, a solution of polyvinyl alcohol in water is sprayed and is visualized using a high-speed camera. The droplet size distribution is studied from simulations with experiments for three spray cases: electrospray, air spray, and air-controlled electrospray. Our simulations and experiments reveal that the electric field is effective in reducing the droplet size, while air flow offers more jet break-ups and thus a larger number of droplets. As a result, air-controlled electrospray where these two driving forces are synergistically combined leads to a larger number of smaller droplets than electrospray or air spray. Finally, we applied three spray processes to obtain a deposition of sulfur/mesoporous carbon/graphene/polymer binder composites as a lithium sulfur battery cathode and demonstrated that air-controlled electrospray leads to a higher capacity and rate capability than other processes, exhibiting 800 mA h g⁻¹ at 0.5C and 600 mA h g⁻¹ at 2C.