Poly(lactic-co-glycolic acid) (PLGA) and poly(caprolactone-co-glycolic acid) (PCLGA) solutions were electrospun into membranes with tailored fiber diameter of 1.8 μm. This particular fiber diameter was tuned depending on the used co-polymer by adjusting the electrospinning parameters that mainly influence the fiber diameter. The greatest setting of the fiber diameter was achieved by varying the polymer solution parameters (polymer concentration, solvents and solvents ratio). PLGA was adequately electrospun with 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), whereas PCLGA required a polar solvent (such as chloroform) with a lower dielectric constant. Moreover, due to the amorphous morphology of PCLGA, pyridine as salt had to be added to the starting solution to increase its conductivity and make it electrospinnable. Indeed, the electrospinning of this co-polymer presents notable difficulties due to its amorphous structure. Interestingly, PCLGA, having a higher glycolic acid molar fraction than commonly electrospun co-polymers (caprolactone:glycolic acid ratio of 45:55 instead of 90:10), could be successfully electrospun, which has not been reported to date. To an accurate setting of fiber diameter, the voltage and the distance from needle to collector were varied. Finally, the study of the surface tension, conductivity and viscosity of the polymer solutions allowed to correlate these particular characteristics of the solutions with the electrospinning variables so that prior knowledge of them enables predicting the required processing conditions.