The crystallinity of the homopolymers and PEDOT-PCL scaffold was evaluated using PXRD (Fig. ). Pristine PEDOT was totally amorphous exhibiting a broad peak centered at 2θ = 24 o corresponding to stacking of the aromatic units with a distance of d 4.5 Ǻ 72 . Pristine PCL, on the other hand, exhibited a semi-crystalline character with two sharp peaks at 2θ = 21.4 o and 23.7 o , which are assigned to (110) and (200) planes, respectively, and are in good agreement with the PCL literature . While most of the previously synthesized PCL revealed almost pure crystalline character, photochemically synthesized PCL using DPIBr had a more amorphous character. This is due to decreased crystallinity of PCL with increasing molecular weight. Moreover, a slight shift can be observed in the powder diffractogram of PEDOT-PCL (Figure inset) compared to PCL. This result also supports the chemical incorporation of PEDOT into PCL. We then employed thermal analysis of PEDOT, PCL, and PEDOT-PCL scaffold using DSC (Fig. ) and TGA (Fig. ), respectively. Pristine PCL exhibited an endothermic peak at 63.4 o C corresponding to the typical melting point (m) of PCL . PEDOT displayed a broad endotherm starting from 80 o C. This is due to the removal of bromide ions from the polymer during heating and was previously encountered . On the other hand, the PEDOT-PCL scaffold exhibited double melting points; one major endothermic peak at 53.7 o C with a shoulder at 46 o C. Such observation was previously and this shift to lower m was attributed to the chemical incorporation of PEDOT to PCL resulting in the formation of less crystalline material that melts at significantly lower temperatures . Contrary to the PCL literature, during the cooling process, no glass transition was observed. This could be attributed to the semicrystalline nature of the synthesized PCL. According to the enthalpy found using DSC, the degree of crystallinity (Xc) was calculated to be 15.7 from the following equation: Xc = (ΔH m / ΔH 0 ) x 100 where ΔH m is the melting enthalpy and ΔHm is the fusion enthalpy of pure crystalline PCL with the value of 136 J/g (Fig ) . The TGA result of pristine PEDOT (Fig. ) reveals a significant weight loss until 150 o C due to the removal of dopant ions (bromide), as such weight loss was previously observed in PEDOT produced by the same photoinduced step-growth polymerization . After the removal of the dopant ions, PEDOT can be considered as thermally stable up until 400 o C where a sudden weight loss occurs due to the thermal decomposition yielding 40% char. TGA thermogram of PCL exhibits the first 5% weight loss at 100 o C due to possible evaporation of a trace amount of moisture and absorbed solvent. The melting point of PCL around 54 o C can easily be observed in the differential thermal analysis (DTA) data (Fig. ). Pristine PCL can be considered a stable polymer until 400 o C, which is in agreement with the literature . At 400 o C, a sudden decomposition of PCL occurs which results in 0% char yield after 500 o C. TGA of PEDOT-PCL scaffold reveals its thermal stability (first 5% weight loss) until 200 o C. The higher thermal stability of PEDOT-PCL can be attributed to the decreased amount of bromide ions present in the scaffold since most of the HBr released is used for the ROP of ECL. Gradual weight loss occurs until 390 o C where thermal decomposition of the scaffold starts yielding 20% char at 900 o C. In short, the thermal stability of the photochemically fabricated PEDOT-PCL scaffold exhibits the average of the thermal stabilities of the two homopolymers (pristine PEDOT and PCL).