Natural fibers have attracted increasing interest as an alternative to produce environmentally friendly and sustainable materials. Particularly, hemp fibers have been widely used in various industrial applications due to their extremely unique properties. However, hemp can generate a large amount of agro-waste, and it results in an attractive source of biopolymers for the development of low-cost materials as an alternative to the raw materials and conventional petroleum-based plastics. In addition, deep eutectic solvents (DESs), a new type of truly green solvents, have been shown to remove gums, lignin, and other non-cellulosic components from hemp fibers. Reusing these components dissolved into the DESs to fabricate new materials directly by electrospinning is a very attractive but still unexplored endeavor. Thus, this innovative research to venture new upcycling pathways is focused on the fabrication of composite nanofibers by electrospinning of a gel-based blend of Poly(vinyl alcohol) (PVA) and hemp agro-waste (HW) dissolved into choline chloride (ChCl):Glycerol (1:2) and ChCl:Urea (1:2) DES mixtures. The results obtained revealed that the produced nanofibers displayed uniform appearance with diameters ranging from 257.7 ± 65.6 nm to 380.8 ± 134.0 nm. In addition, the mechanical properties of the electrospun composite nanofibers produced from the gel-based blends of HW dissolved in DESs and PVA (HW-DESs_PVA) were found to be superior, resulting in an enhanced tensile strength and Young's modulus. Furthermore, the incorporation of HW into the nanofibers was able to provide bioactive antioxidant and antibacterial properties. Overall, this study demonstrated a promising, more sustainable, and eco-friendly way to produce electrospun composite nanofibers using HW in a circular economy perspective.