Electrospun polymer nanofiber materials have been studied as basic materials for various applications. Depending on the intended use of the fibers, their morphology can be adjusted by changing the technological parameters, the properties of the spinning solutions, and the combinations of composition. The aim of the research was to evaluate the effect of electrode type, spinning parameters, polymer molecular weight, and solution concentration on membranes morphology. The main priority was to obtain the smallest possible fiber diameters and homogeneous electrospun membranes. As a result, five electrode types were selected, the lowest PVA solution concentration for stable spinning process was detected, spinning parameters for homogenous fibers were obtained, and the morphology of electrospun fiber membranes was analyzed. Viscosity, conductivity, pH, and density were evaluated for PVA polymers with five different molecular weights (30–145 kDa) and three concentration solutions (6, 8, and 10 wt.%). The membrane defects and fiber diameters were compared as a function of molecular weight and electrode type. The minimum concentration of PVA in the solution allowed more additives to be added to the solution, resulting in thinner diameters and a higher concentration of the additive in the membranes. The molecular weight, concentration, and electrode significantly affected the fiber diameters and the overall quality of the membrane.