This paper provides a viewpoint of the technology of the fast-scanning calorimetry with the relaxation behavior of disordered side chains of poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-C12) around the glass transition temperature of the side chains (T_g,γ). PBTTT is an ideal model of the high-performance copolymer of poly(alkylthiophenes) with side chains. The γ₁ relaxation process of the disordered side chains of PBTTT was detected as a small endothermic peak that emerges before the γ₂ relaxation process. It shows an increase with increasing temperature as it approaches the glass transition temperature of the disordered side chains of PBTTT. The ductile–brittle transition of PBTTT in low temperatures originating from the thermal relaxation process is probed and illustrated by physical aging experiments. The signature is shown that the relaxation process of the disordered side chain of PBTTT at low temperatures varies from Arrhenius temperature dependence to super Arrhenius temperature dependence at high temperatures. These observations could have significant consequences for the stability of devices based on conjugated polymers, especially those utilized for stretchable or flexible applications, or those demanding mechanical robustness during tensile fabrication or use in a low-temperature environment.