Under certain conditions algal alginates bind pinacyanol chloride in the form of dimers – this is the conclusion drawn from a uv/vis and circular dichroism (CD) spectroscopic study of aqueous solutions of the dye in a 10-fold molar excess of the polysaccharide from different sources. With its easily detected features the dimer holds promise as a diagnostic tool for alginate conformational analysis. Binding of the strongly blue-shifted (maximum wavelength = 485 nm) dimer is probably mediated by the charged groups and involves guluronate units only. By using the peakFit program, the two overlapping excitonic absorption bands together with the optically inactive band resulted from the interaction of pinacyanol with a specific alginate concentration were separated. The standard Gibbs energy of the interaction was calculated as –27.02 kJ^.mol–1. The dimers are sensitive against acid and divalent cations