To prepare electrospun fibres from phenol liquefied wood (LW), polyvinyl pyrrolidone (PVP) with an average molecular weight of 1,300,000 g/mol was considered as an additive to synthesize the electrospinning solution. Following this, electrospinning was carried out. Next, the morphologies of the electrospun fibres and properties of the electrospinning solution were investigated. The results showed that fibres derived from liquefied wood via an electrospinning process could be obtained satisfactorily by synthesizing the electrospinning solution. The morphologies of the electrospun fibres with diameters of around 2.0 mu m were favourable as liquefied wood, and 6%PVP/ethanol solution was mixed at a ratio of 1: 1 by weight. With the increasing concentration of liquefied wood, the surface tension of the electrospinning solution increased from 0.022 N/m to 0.033 N/m. Additionally, the conductivity increased on a small scale. Furthermore, when the liquefied wood was added to the PVP/ethanol solution, more micro-molecules were introduced into the mixture, thus the viscosity decreased significantly due to the attenuation of PVP.