© 2014 American Chemical Society. We investigate the role of molecular weight (MW) of the photoactive polymer poly(3-hexylthiophene) (P3HT) on the temperature-dependent decohesion kinetics of bulk heterojunction (BHJ) organic solar cells (OSCs). The MW of P3HT has been directly correlated to its carrier field effect mobilities and the ambient temperature also affects OSC in-service performance and P3HT arrangement within the BHJ layer. Under inert conditions, time-dependent decohesion readily occurs within the BHJ layer at loads well below its fracture resistance. We observe that by increasing the MW of P3HT, greater resistance to decohesion is achieved. However, failure consistently occurs within the BHJ layer representing the weakest layer within the device stack. Additionally, it was found that at temperatures below the glass transition temperature (∼41-45 °C), decohesion was characterized by brittle failure via molecular bond rupture. Above the glass transition temperature, decohesion growth occurred by a viscoelastic process in the BHJ layer, leading to a significant degree of viscoelastic deformation. We develop a viscoelastic model based on molecular relaxation to describe the resulting behavior. The study has implications for OSC long-term reliability and device performance, which are important for OSC production and implementation.