2-Hydroxymethylthiophene and its acetate were placed in acidic organic media of various natures and strengths and at different temperatures. Polycondensations involving the alcohol or acetate function and a thiophene proton only occurred if the solutions were heated and the acid concentration was relatively high. The thorough assessment of the structure of the ensuing polymers, including those arising from differently methylated derivatives of the parent structures, indicated that the electrophilic substitutions had taken place at all free thiophene sites and that conjugated sequences had also formed. The kinetic and mechanistic features of these systems are examined and discussed in comparison with those displayed by furfuryl alcohol.