The genus Rhododendron is an ancient and most widely distributed genus of the family Ericaceae consisting of evergreen plant species that have been utilized as traditional medicine since a very long time for the treatment of various ailments including pain, asthma, inflammation, cold, and acute bronchitis. The chemistry of polyphenolics isolated from a number of species of the genus Rhododendron has been investigated. During the currently designed study, an in-depth study on the phytochemistry, natural distribution, biosynthesis, and pharmacological properties including their potential capability as free radical scavengers has been conducted. This work provides structural characteristics of phenolic compounds isolated from the species of Rhododendron with remarkable antioxidant potential. In addition, biosynthesis and theranostic study have also been encompassed with the aims to furnish a wide platform of valuable information for designing of new drug entities. The detailed information including names, structural features, origins, classification, biosynthetic pathways, theranostics, and pharmacological effects of about 171 phenolics and flavonoids isolated from the 36 plant species of the genus Rhododendron with the antioxidant potential has been covered in this manuscript. This study demonstrated that species of Rhododendron genus have excellent antioxidant activities and great potential as a source for natural health products. This comprehensive review might serve as a foundation for more investigation into the Rhododendron genus.