We produced defect-free electrospun fibers from aqueous dispersions of lignin, poly(vinyl alcohol) (PVA), and cellulose nanocrystals (CNCs), which were used as reinforcing nanoparticles. The thermomechanical performance of the lignin-based electrospun fibers and the spin-coated thin films was improved when they were embedded with CNCs. Isochronal dynamic mechanical analysis (DMA) was used to assess the viscoelastic properties of the lignin:PVA electrospun fiber mats loaded with CNCs. DMA revealed that α relaxation processes became less prominent with an increased lignin content, an effect that correlated with the loss tangent (tan δ = E″/E') and α peak (Tg) that shifted to higher temperatures. This can be ascribed to the restraint of the segmental motion of PVA in the amorphous regions caused by strong intermolecular interactions. The reinforcing effect and high humidity stability attained by addition of CNCs (5, 10, or 15 wt %) in the multicomponent fiber mats were revealed. Nanoindentation was performed to assess the elastic modulus and hardness of as-prepared and cross-section surfaces of spin-coated lignin:PVA (75:25) films loaded with CNC. The properties of the two surfaces differed, and only the trend in cross-section elastic modulus correlated with DMA results. After addition of 5 wt % CNCs, both the DMA and nanoindentation elastic modulus remained constant, while after addition of 15 wt % CNCs, both increased substantially. An indentation size effect was observed in the nanoindentation hardness, and the results provided insight into the effect of addition of CNCs on the microphysical processes controlling the yield behavior in the composites.