Polyphenylenes (PPs) represent a class of conjugated polymers that have been used in applications ranging from organic electronic devices, sensors, polymer film additives to manipulate their mechanical properties, and even fluorescent tags or nanocarriers in biological media.1-3 The versatility of PPs stem from innovative synthetic strategies that have evolved throughout the years to provide avenues that precisely tune their architecture and function for specific purposes. This Review will cover the state of the art research on various PPs related to the relationship between their structure and resulting properties.