Green poly(ethylene oxide) (PEO)/cellulose nanocrystals (CNCs)/poly(vinylpyrrolidone) (PVP) composites were prepared via electrospinning technique. The use of PVP and/ or CNCs improved the overall thermal stability and mechanical properties of the PEO fibers. A strong synergistic reinforcing effect was achieved when PVP polymer and CNCs were combined in the composite. This synergistic reinforcement was accompanied with the formation of unique fiber-bead-fiber morphology. The beads were elongated and orientated along the applied force direction during tensile testing, providing an energy dissipation mechanism and a positive reinforcement effect. The combination of CNCs with PVP induced special chemical interactions, and distracted the interactions between PVP and PEO. As a result, the crystallinity of PEO was increased in the system, which also helped enhance fiber properties. The approach developed in this work offers a new way for reinforcing electrospun PEO-based composite fibers for sustainable green composite development.