Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) was synthesized and subsequently neutralized with various acids to form PDMAEMA center dot HCl, PDMAEMA center dot HBF4, and PDMAEMA center dot HOTf polyelectrolytes. In addition, ion exchange of the chloride anion provided polyelectrolytes with NO3-, N(CN)(2)(-), PF6-, and Tf2N-anions. The glass transition temperature (T-g) varied significantly with anion in the order Cl- > PF6- > BF4- > NO3- > TfO- > Tf2N-. The polyelectrolytes with larger, weakly coordinated anions required less thermal energy to dissociate ionic interactions, leading to tailored thermal behavior. Solution conductivity of the water-soluble polyelectrolytes decreased in the order Cl- > NO3- > BF4- > N(CN)(2)(-) > TfO-, which was consistent with counteranion mobility. Solution rheology revealed polyelectrolyte behavior for PDMAEMA center dot HCl, PDMAEMA center dot HBF4, and PDMAEMA center dot HOTf. PDMAEMA center dot HCl underwent an electrospraying-electrospinning transition at three times the critical concentration for entanglement (C-e), which was consistent with other cationic polyelectrolytes. However, the BF4-and TfO- polyelectrolytes exhibited an onset of fiber formation at (1.4-1.8)C-e, much closer to the behavior of neutral, nonassociating polymers. Fiber diameters for all polyelectrolytes were 1-2 orders of magnitude smaller than those for neutral polymers due to increased conductivities of the electrospinning solutions.