Schottky and heterojunction diodes were fabricated using high tensile strength polymers. The heterojunction diode was fabricated by sequential electrochemical polymerisation of 3-methyl thiophene and 3-octyl thiophene on an indium-tin oxide (ITO) coated glass substrate. The high tensile strength enabled the bilayer (used in heterojunction diodes) or the poly 3-octyl thiophene films (used in the Schottky diodes) to be peeled of from the substrate and sandwich it between any two desired metals. It was found that the Schottky diodes of ITO (or Si)/POT/ Al (or Zn) exhibit moderate rectifying behaviour and ITO (or Si)/POT/Cu devices exhibit ohmic contact. The POT/PMT heterojunction diode showed excellent rectification effect when sandwiched between any two metals irrespective of their work function. This shows that the results observed were solely due to the polymer/polymer interface. The Cu/POT/PMT/Cu heterojunction system was used in this study. The carrier-flow of the two semiconductors in the Cu/POT/PMT/Cu heterojunction diode was discussed in details. The rectification ratio, the barrier height, and the ideality factor for the heterojunction diode were found to be 64 (+/-1.2 V), 0.81 eV, and 5.7 under ambient conditions, respectively. Some of the important energy band parameters were also determined.