A review with 36 refs. covering the synthesis routes to polyphenylenes, e.g., the Friedel-Crafts reactions, oxidative cationic polymerization of benzene in the presence of AlCl3/CuCl2, anionic polymerization in the presence of BuLi, the Yamamoto reaction, Diels-Alder reactions, etc. The products show broad MWD, various isomeric forms, colors, etc. Physicochemical properties (crystallinity, solubility, thermal resistance, electric conductivity) are described in relation to chemical structure. Service properties of construction materials (pump and mixer parts, anticorrosive and ablative coatings) produced from poly(p-phenylene)s (I) are also characterized. As the chain length is increased, the solubility and the melting temperature of linear I decreases and increases, resp. Conventional processing procedures are inapplicable to I. Powdered I compacted at 520 MPa at room temperature and sintered in nitrogen at 500degreesC and 140 Mpa for 1 h, yielded a product resistant to high-T hydrolysis and chemical agents. Polycondensation (300degreesC) of terphenyl with m-benzene disulfone chloride afforded soluble oligo(phenylene)s; these dissolved in organic solvents serve as adhesives in the production of laminates. Extremely pure I is applied as a (semi)conductor.