Ultrafine nanoporous copper (UNP Cu) with a characteristic pore size of about 12 nm and a ligament size of about 14 nm was fabricated from amorphous Mg65Cu25Y10 precursor alloys after dealloying in a 0.1 M H₂SO₄ solution modified by poly(vinyly alcohol) polymers with a molecular weight of 105000 g/mol (PVA-124). The suppression of the surface diffusion from PVA-124 reduced the size of the nanopores and ligaments to 20 nm when the concentration of the added PVA-124 exceeded 0.1 g L-1. When the concentration of the added PVA-124 exceeded 2 g L-1, PVA-124 triggered the polymerization process. The resultant polymer surface layer on the fcc Cu ligaments was shown to reduce the rate of selective dissolution. It was also shown that extending the immersion time resulted in a suppression of coarsening. The introduction of PVA-124 polymer into acids resulted in a higher viscosity of the dealloying solutions, particularly when the concentration of PVA-124 was higher than 1.0 g L-1. This viscosity was shown not only to reduced rate of diffusion of Cu adatoms in PVA-124 solutions, but also forced the accumulation of Cu adatoms to form small scale UNP Cu.