Spin‐coating a mixture solution of P3HT and PCBM on a cold substrate largely enhanced the power conversion efficiency (PCE) of the bulk heterojunction (BHJ) solar cells. This concept was based on the abrupt decrease in the solubility of P3HT as solution temperature decreased. The selective precipitation of P3HT on the PEDOT:PSS‐coated cold substrate facilitated a desirable rich composition of P3HT at the interface with the PEDOT:PSS layer. The high crystallinity of P3HT suppressed the movement of PCBM during thermal annealing, preventing aggregation of PCBM. The morphological excellence of the pristine film gave a comparable PCE to that made by the conventional fabrication process. After thermal annealing, the device made via coating on a cold substrate showed above 30% increase in PCE from the BHJ solar cells made by the conventional method.
