This article reports on electrospun poly(vinyl alcohol) (PVA) modification with lignocellulose nanowhiskers (LCNWs) produced from hemp shives without using harsh preparation steps. LCNWs were obtained by using steam explosion (SE) pretreatment, ball milling, and ultrasonication. Formation of LCNWs was confirmed by atomic force microscopy. Obtained LCNWs were used to modify the mechanical properties of electrospun PVA nanofibers. Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy analyses provided clear evidence of the presence of cellulose nanowhiskers in the PVA/LCNW electrospun mats. It was found that tensile stress at break increases more than fivefold for PVA nanofiber mats reinforced with LCNWs.