Proton spin-lattice relaxation time, T1, and chemical shift of solvent protons (dichloroacetic acid–chloroform or dichloroethane) were measured on poly(γ-methyl-L-glutamate) (PMLG) solutions. It was found that T1 and chemical shift were considerably affected by the conformational transition of PMLG, and peculiar behavior did exist. These were discussed in relation to the results on the solvent mixtures. The order of the magnitudes of the interactions between PMLG and the solvent molecules was found to be as follows: carboxyl proton of dichloroacetic acid (DAC) acting as a random-coil solvent>>methine group of DCA>helix-forming solvent.It was proposed in connection with the results on amide solutions that the interaction between PMLG and DCA should be a weak hydrogen bonding rather than protonated form interactions. We also measured the dependence of T1 on PMLG concentration, and discussed the results in terms of PMLG–solvents and PMLG–PMLG intermolecular interactions.