We report the concise synthesis of a symmetrical monomer that provides a head-to-head pyridine building block for the preparation of cationic conjugated polymers. The obtained poly(pyridinium-phenylene) polymers display appealing properties such as high electron affinity, charge-transport upon n-doping, and optical response to electron-donating analytes. A simple assay for the optical detection of low micromolar amounts of a variety of analytes in aqueous solution was developed. In particular, caffeine could be measured at a 25 μM detection limit. The reported polymers are also suitable for layer-by-layer film formation.