The chitosan(CS)/polyvinyl alcohol(PVA) spinning solution was prepared using acetic acid(HAc) as solvent. The steady-state rheological and dynamic rheological properties were investigated, and the feasibility of electrospinning was examined. The results showed that with the increase of CS mass fraction, the consistency coefficient, structural viscosity index, apparent viscosity, storage modulus(G′), loss modulus(G″) and composite viscosity(η*) of the spinning solution increased accordingly, while the non-Newtonian index decreased accordingly, which was not conducive to the electrospinning of CS/PVA spinning solution. With the increase of the test temperature, the consistency coefficient, structural viscosity index, apparent viscosity, G′, G″nd η* of the spinning solution decreased correspondingly, whereas the non-Newtonian index increased, the flow performance of the spinning liquid was strengthened and the spinnability was improved. When the mass fraction of CS was 3.0%, the apparent viscosity, consistency coefficient and structural viscosity index of the spinning solution at the test temperature of 30 ℃ were small, which were 1.650 Pa·s, 7.978 1 and 2.16, respectively, and the non-Newtonian index was 0.887 7 close to 1, indicating that the spinning solution had good fluidity and processability. Combined with SEM and rheological behavior analysis, under room temperature the CS/PVA spinning solution with a CS mass fraction of 3.0% exhibited excellent spinnability and could construct continuous, uniform nanofibers without beaded connections.