A new polythiophene containing a cholesteryl side chain in the β-position was chemically polymerised in nitromethane/carbontetrachloride using FeCl3 as the oxidizing agent. Polymerisation was also achieved by constant current electrolysis in dichloromethane. Subsequently, conducting copolymers of thiophene-3-yl acetic acid cholesteryl ester (CM), PCM1 (obtained from chemical polymerisation method) and PCM4 (obtained from constant current electrolysis) with pyrrole were synthesized using p-toluene sulfonic acid and sodium dodecyl sulfate as the supporting electrolytes via constant potential electrolyses. Characterizations of the samples were performed by CV, FTIR, NMR, DSC, TGA and SEM analyses. Electrical conductivities were measured by the four-probe technique.