Salix holocellulose liquefaction products (SHLP) were prepared by liquefaction of the wood. A spinning solution of polyurethane (PU) and SHLP was prepared, and microspheres were obtained by electrospinning. The bonding of SHLP and PU-SHLP was characterized via FTIR. The conductivity and viscosity of spinning solution were characterized by conductivity meter and viscosity meter, respectively. The electrospun fiber morphologies were characterized by SEM. The results showed that PU was introduced into SHLP. The concentration of solution was the main factor that affected the morphology of microspheres, and the diameters of microspheres was from 0.18 to 1.18 μm. In addition, in this electrospinning system, the concentration of liquefied products in the mixed spinning solution was the major factor that affected the morphology of microfibers, and the diameters of microfibers were from 0.29 to 1.78 μm.