In the study, we successfully dissolved beta-CD using an ionic liquid without molecular modification and electrospun the solution without polymer carriers. The XRD of the resulting fiber confirmed that beta-CD molecules self-assembled and aggregated to form the fiber. The spinning conditions showed significant influences on the spinnability and fiber formation. The addition of DMF decreased the solution viscosity and made the jet stable, which resulted in the spinnability improvement and the decrease of fiber diameter and its standard deviation.