Nowadays, polypropylene-based nonwovens are used in many areas, from filtration to medicine. One of the methods for obtaining such materials is melt electrospinning. In some cases, it is especially interesting to produce composite fibers with a high degree of filling. In this work, the influence of the filling degree of isotactic polypropylene with calcium carbonate on the structure and properties of nonwoven materials obtained by melt electrospinning was studied. It was shown that electrospinning is possible, even at a filler content of 50%, while the average diameter of the fibers increases with the growth in the content of calcium carbonate. The addition of sodium stearate significantly reduces the diameter of the fibers (from 10–65 to 2–10 microns) due to reducing viscosity and increasing the electrical conductivity of the melt. Wide-angle X-ray diffraction analysis and IR spectroscopy reveal that the initial polymer and composites are characterized by the presence of stable α-form crystals, while nonwovens show a predominance of smectic mesophase. The addition of calcium carbonate leads to an increase in the hydrophobicity of the composite films, the addition of sodium stearate results in a decrease of hydrophobicity, while all nonwovens demonstrate superhydrophobic properties.