1D poly(3,4-ethylenedioxythiophene) (PEDOT) nanomaterials, including ellipsoidal nanoparticles, nanorods, and nanotubes, are fabricated via chemical oxidation polymerization in reverse (water-in-oil) microemulsions. The reverse cylindrical micelles are prepared with sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and aqueous FeCl3 solution in hexane. The morphology of the final products is determined by carefully tuning the degree of oxidation potential at the micelle surface. Notably, the fabrication of gram-scale amounts of products is possible under optimized synthetic conditions, suggesting that this methodology is appropriate for the large-scale production of the corresponding nanomaterials. The as-prepared PEDOT nanomaterials are applied to the precise detection of alcohol vapors. The chemical sensors based on the PEDOT nanomaterials present excellent reversibility and reproducibility in response.