Polymer/polymer nanocomposites based on high-density polyethylene (HDPE) and biocompatible polyvinyl alcohol (PVA) were prepared by tensile drawing of HDPE in the PVA solutions via environmental crazing. The mechanism of this phenomenon was described. The HDPE/PVA nanocomposites were studied by the methods of scanning electron microscopy, atomic force microscopy, gravimetry, tensile tests, and their composition, properties, and performance were characterized. The content of PVA in the HDPE/PVA nanocomposites (up to 22 wt.%) was controlled by the tensile strain of HDPE and concentration of PVA in the solution. Depending on the content of PVA, the wettability of the HDPE/PVA nanocomposite (hydrophilic-lipophilic balance) could be varied in a broad interval from 45 to 98°. The modification of HDPE by the biocompatible PVA offers a beneficial avenue for practical applications of the HDPE/PVA composites as biomedical materials, packaging and protective materials, modern textile articles, breathable materials, membranes and sorbents, etc.