To further mitigate the phosphoric acid leakage in high temperature proton exchange membrane (PEM), the microporosity of Tröger's base (TB) membrane based on a V-shaped bridged bicyclic diamine has been fine-tailored readily by polymeric blending with a miscible polymer of intrinsic microporosity (PIM-1). As expected, the average cavity radius in the range of 3.46–4.21 Å has been achieved when the blending ratio of PIM-1 increases from 5 to 20 mol% due to the interaction between the amine group of TB and the nitrile group of PIM-1. The resulting PEMs show excellent PA retention ability. Notably, PIM/TB9 membrane with a suitable cavity radius of 3.5 Å and largest FFV4 of 49.1% exhibits an exciting PA retention of about 80%, which is much better than the pristine TB membrane. Thus, the remaining proton conductivity of PIM/TB9 is almost 5 times higher than that of TB membrane after 22 relative humidity cycle tests. Moreover, the resulting cell can run smoothly within a wide temperature range from 0 to 160 °C. The single cell performs for over 150 AST cycles and remains stable for >600 h with no visible voltage decay at 80 °C. Therefore, these results indicate the technical feasibility to improve the PA retention via fine-tuning the intrinsic microporosity of the PEMs through a direct blending method.