The influence of solvent mixtures on electrospinning polymer solutions plays a crucial role in both the electrospinning process and the characteristics of the resulting fibers. Solvents with varying properties can be used to optimize thermodynamic stability, viscosity, evaporation rate, and dielectric constant of a solution simultaneously. This study investigates the fabrication of highly porous poly-2,6-diphenyl-p-phenylene oxide (PPPO) fibers via electrospinning from binary and ternary solvent mixtures. The resulting fibers exhibit significant porosity both at the surface and in the core, as evidenced by their high surface area and textured morphology. These features render the fibers highly effective for sampling volatile organic compounds (VOCs). Adsorption performance is evaluated under passive and dynamic conditions using Musk Xylene as a simulant. Compared to granular PPPO, the fibrous membranes achieved nearly a fourfold increase in passive adsorption and an sevenfold increase in dynamic adsorption. These findings highlight the potential of PPPO electrospun fibers as superior materials for VOC sampling applications.