Fully aromatic, organic polymers have the advantage of being composed from light, abundant elements, and are hailed as candidates in electronic and optical devices "beyond silicon", yet, applications that make use of their pi-conjugated backbone and optical bandgap are lacking outside of heterogeneous catalysis. Herein, we use a series of sulfur- and nitrogen-containing porous polymers (SNPs) as real-lime optical and electronic sensors reversibly triggered and reset by acid and ammonia vapors. Our SNPs incorporate donor-acceptor and donor-donor motifs in extended networks and enable us to study the changes in bulk conductivity, optical bandgap, and fluorescence lifetimes as a function of pi-electron de/localization in the pristine and protonated states. Interestingly, we find that protonated donor-acceptor polymers show a decrease of the optical bandgap by 0.42 to 0.76 eV and longer fluorescence lifetimes. In contrast, protonation of a donor-donor polymer does not affect its bandgap; however, it leads to an increase of electrical conductivity by up to 25-fold and shorter fluorescence lifetimes. The design strategies highlighted in this study open new avenues toward useful chemical switches and sensors based on modular purely organic materials.