As the power conversion efficiency of organic photovoltaic has been dramatically improved to over 18%, achieving long-term stability is now crucial for applications of this promising photovoltaic technology. Among the high-efficiency systems, most are using BTP-4F and its analogs as acceptors. Herein, we determine the thermal transition temperatures (Tg) of seven BTP analogs to develop a structure-Tg framework. Our results point out an unresolved molecular design conundrum on how to simultaneously achieve high performance and intrinsic stability with BTP-based acceptors. We also show that PC71BM has miscibility above the percolation threshold in PM6 and can maintain local charge percolation and improved stability in ternary devices. However, PC71BM is not miscible with BTP-C3-4F and unfavorable vertical gradients that develop during aging still degrade performance. This points to a second thermodynamic conundrum. A compound with differential miscibility in the donor polymer can only impact percolation, and a compound with differential miscibility with the BTP only impacts diffusion.