The doubly oxonium-embedded picenes have been synthesized for the first time. They have a rigid planar electron-deficient core and are stabilized by the pyrylium aromaticity. The doping positions of oxygen atoms influenced their electrochemical and optoelectronic properties because of the different charge distributions in the skeletons. The donor-acceptor-donor-type molecules baring electron-donating triphenylamine moieties exhibited intramolecular charge-transfer absorption at the visible regions, indicating the large impact of the substituents on their electronic properties.