PVA and PA-66 nanocomposite fibers with montmorillonite were prepared by electrospinning. Mixing of the components was conducted in two ways: polymer and montmorillonite were mixed with solvent, or monomer was I polymerized in the presence of montmorillonite and was then dissolved in a solvent. Polymer/montmorillonite solutions were then electrospun on a non-woven substrate. To the unaided eye, the coated area was either continuous coating or well-defined spots. Characterization of the fiber structure and the particle size and distribution by SEM and elemental analysis showed the nanosized filler to be dispersed through the fiber network of the polymer/nanocomposite regardless of the preparation method. However, the clay particles within the fibers were smaller with the polymerization method than mixing in solvent. Only the PA-66-based nanocomposites exhibited large enough coating area on the substrate for measurements of contact angles and the time required for water penetration. Contact angles and the time required for water penetration were increased for most of the PA/nanoclay composites relative to the uncoated substrate.