A strategically designed polymer semiconductor thin film morphology with both high responsivity to the specific gas analyte and high signal transport efficiency is reported to realize high-performance flexible NOx gas sensors. Breath-figure (BF) molding of polymer semiconductors enables a finely defined degree of nano-porosity in polymer films with high reproducibility while maintaining high charge carrier mobility characteristics of organic field effect transistors (OFETs). The optimized BF-OFET with a donor-acceptor copolymer exhibits a maximum responsivity of over 104%, sensitivity of 774% ppm-1, and limit of detection (LOD) of 110 ppb against NO at room temperature. When tested across at NO concentrations of 0.2-10 ppm, the BF-OFET gas sensor exhibits a response time of 100-300 s, which is suitable for safety purposes in practical applications. Furthermore, BF-OFETs show a high reproducibility as confirmed by statistical analysis on 64 independently fabricated devices. The selectivity of NOx analytes is tested by comparing the sensing ability of BF-OFETs with those of other reducing gases and volatile organic compounds; the BF-OFET gas sensor platform monitors specific gas analytes based on their polarity and magnitude of sensitivity. Finally, flexible BF-OFETs conjugated with plastic substrates are demonstrated and they exhibit a sensitivity of 500% ppm-1 and a LOD of 215 ppb, with a responsivity degradation of only 14.2% after 10 000 bending cycles at 1% strain.