Electrogenerated films of polypyrrole were degraded (overoxidized) by consecutive short anodic polarizations at 900 mV. The degree of degradation was quantified by means of the percentage of anodic voltammetric charge lost after each consecutive degradation processes. The charge consumed to compact 1 mol of polymeric segments (molar compaction charge) was obtained for every degraded state from experimental series of chronoamperograms, as indicated by the electrochemically stimulated conformational relaxation model. The molar magnitude decreases linearly with the change on the degradation percentage indicating the presence of shorter ideal lineal chains on a progressively degraded polymer. The correlation between these magnitudes opens the way to attain new molecular magnitudes of the polymeric chains by electrochemical measurements, as predicted by the model. (c) 2006 Elsevier Ltd. All rights reserved.