The conformational changes of poly-jV5-(4-hydroxybutyl)-L-glutamme have been investigated in the LiCl-methanol solvent system. Optical rotatory dispersion (ORD) measurements indicate that, with increasing LiCl concentration, an -helix-to-random coil transition takes place, its midpoint being at about 3 M LiCl. Intrinsic viscosity measurements, on the other hand, reveal two transitions. The first, in the range 2-4 M salt, is associated with a decrease in viscosity, as expected for the rod-like to disordered chain transformation suggested by the ORD data. The second, in the range 4-6 M salt, is characterized by an increase of viscosity, i.e., a change in the opposite direction. It is proposed that the polypeptide binds Li+ ions, thus acquiring polyelectrolyte character.