Blending lignin as the second most abundant polymer in nature with nanostructured compounds such as dendritic polymers will not only add value to lignin, but also increase its application in various fields. In this study, softwood Kraft lignin/polyamidoamine dendritic polymer (PAMAM) blends were fabricated by solution electrospinning method to produce bead-free nanofiber mats. The mats were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), zeta potential, and thermogravimetry analysis (TGA). The chemical intermolecular interactions between lignin functional groups and abundant amino groups in PAMAM were investigated by FTIR and viscosity measurement. These interactions enhanced the mechanical and thermal characteristics of lignin/PAMAM mats, providing further potential applications at industry level.