Silicone fibers were synthesized by electrospinning, where 17 solvents with different chemical properties (boiling point, conductivity, viscosity, dielectric constant, and solubility parameter) were used to dissolve the silicone polymer for the formation of fibers through electrospinning. Previous reports on the miniaturization of fibers of polymers dissolved in a solvent suggested that the low viscosity and the high conductivity of the polymer solution were the key parameters to form thinner fibers when using a single solvent. Here we have found a powerful way to search for good solvents to reduce the fiber diameters as well as to dissolve the polymers. By considering different types of solvents, it was found that the solubility parameters conclusively determined the smallest fiber diameters of the silicone polymers. The solubility parameter of the silicone polymer should be lower than those of the solvents to make thinner fibers. The results have revealed the strong relationship between the diameters of the fibers and the solubility parameters of the solvents, and they indicate that the solubility parameter could be a good indicative parameter in selecting solvents during the fabrication of thinner fibers by electrospinning, especially for siloxane polymers.