Summary Fabrication of non-fullerene (NF)-based polymer solar cells (PSCs) has been an arduous task involving various approaches to optimize the morphology of blend film for superior performance. In this work, unique exothermic peaks can be observed in differential scanning calorimetry first heating scan of the blend films, which are assigned to the cold crystallization temperature (TCC) of NF acceptors when blended with different degree of crystallinity polymers, and TCC contains the phase information at quenched stage of the film development. A linear correlation between the phase separation parameters and TCC was established, which helps to select the appropriate donor for a specific acceptor. Utilizing multiple polymer-NF blend systems, we report an expectation TCC value between 210°C and 230°C, which would promise balanced domain size, purity, and consequentially superior performance. Further investigation revealed that TCC can also be used to evaluate the thermal stability.