Potential energy functions evaluating both repulsive-attractive van der Waals non-bonding interactions and electrostatic interactions have been used to evaluate the conformational energies of the repeating units of the kappa-carrageenan polymers. Structural parameters have been obtained by minimization MNDO procedures (MOPAC). Energy maps have been calculated for the (1-3) alpha-D-galactose-4-sulphate (GS) and the (1-4)-3,6-anhydro-alpha-D-galactose (A) residues, taking into account the conformational freedom of the sulphate group. The configurational statistics of the random coiled kappa-carrageenan chain have been explored, disclosing a highly flexible character, which can mainly be ascribed to the random occurrence of two different conformers of the GS-A dimeric unit.