Understanding the effect of conductivity in electrospinning solutions is crucial in order to improve or control the electrospinning process. In this paper the effect of adding small amounts (0.039-0.259 mol . kg(-1)) of three different conductive additives to aqueous solutions of polyvinyl alcohol has been investigated. The salts were HMICl (a room temperature ionic liquid), TEBAC (a quaternary ammonium salt) and KCl. Addition of these salts caused a steady increase in the solution conductivity but the fiber diameter was typically greater than that of PVA alone, and exhibited an oscillatory trend. The oscillatory trend on the fiber diameter is attributed to fiber backbuilding and fusion that occurs prior to deposition on the collector.