Improving the conductivity of electrospinning solutions is often achieved by adding small amounts of conductive additives. HMIMCl, a room temperature ionic liquid, and TEBAC, a quaternary ammonium salt, were added to polylactic acid in chloroform and their effects on solution properties, electrospinning, and fiber properties were investigated. Both additives increased the conductivity which decreased the fiber diameter, but differences were observed on the fiber dispersity and fiber morphology. The conductive solutions caused fiber backbuilding with aggregation and fiber fusion. Reasons for the differences in fiber diameter and fiber morphology are discussed.