The phase diagram for solutions of poly(gamma-benzyl-L-glutamate) in dimethylformamide has been investigated over the entire composition and temperature ranges with dielectric spectroscopy. The dielectric response in this system is dominated by ionic mobility, and phase transitions have been detected as changes in the ionic conductivity. The phase boundaries, determined by dielectric spectroscopy, are consistent with earlier published results obtained by a combination of optical microscopy observations and nuclear magnetic resonance and differential scanning calorimetry studies. (C) 2004 Wiley Periodicals, Inc.