Two of the three conformational polymorphs of dimethyl-3,6-dichloro-2,5-dihydroxyterephthalate are studied by solid-state NMR techniques. The structural differences between the polymorphs have previously been studied by X-ray. In these two polymorphs named white and yellow due to their color, the major structural difference is the torsional angle between the ester group and the aromatic ring. The yellow form has a dihedral angle of 4 degrees between the plane of the aromatic ring and the plane of the ester group, while the white form has two different molecules per unit cell with dihedral angles of 70 degrees and 85 degrees. This change greatly affects the conjugation in the pi-electronic system. In addition, there are differences in the hydrogen-bonding patterns, with the white form having intermolecular hydrogen bonds and the yellow form having intramolecular hydrogen bonds. In this work, the carbon isotropic chemical shift values and the chlorine electric field gradient (EFG) tensor information are extracted from the (13)C MAS spectra, and the principal values of the chemical shift tensors of the carbons are obtained from 2D FIREMAT experiments. Quantum chemical calculations of the chemical shift tensor data as well as the EFG tensor are performed at the HF and DFT levels of theory on individual molecules and on stacks of three molecules to account for the important intermolecular interactions in the white form. The differences between the spectral data on the two polymorphs are discussed in terms of the known electronic and structural differences.