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Soluble main chain phenylene polymers and oligomers are much less well studied than their intractable relative poly(p-Phenylene). This review considers the synthesis and properties of poly(o-phenylene)s, poly(m-phenylene)s, and substituted polyphenylenes with alkyle-, aryl-, carbonyle-, nitro-, halo-, fused aromatic, and ladder containing substituents, together with related compounds. The figure shows a planar polyphenylene derivative that can be obtained as a flexible free-standing film.