<p>The paper analyses the influence of binary solvent systems on the electrospinning process and gelation effect. The characteristics of the electrospinning process are presented, considering the physicochemical properties of polymer solutions and the role of different solvents: chloroform, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and <span>d</span>-limonene. The shift in transition temperatures between the liquid and the gel phase were analyzed, and the obtained fiber structures were assessed using scanning electron microscopy (SEM). The optimization of solvent systems allows for the control of electrospinning process parameters, opening new possibilities for design advanced polymeric materials.</p>