Dimeric forms of flavonoids, known as biflavonoids, are much less studied compared to monomeric forms. It is estimated that nearly 600 different natural biflavonoids have been described to date, containing various subtypes that can be subdivided according to the position of their combinations and the nature of the subunits. The group in which two monomers are linked by a 3'-8″-C atom includes the first isolated biflavonoid ginkgetin, derivatives of amentoflavone, and several other compounds. 3'-8″-biflavones recently attracted much attention as potential molecules with biological activity such as antiviral and antimicrobial activity and as effective molecules for the treatment of neurodegenerative and metabolic diseases and in cancer therapies. With the growing interest in them as pharmacologically active molecules, there is also increasing interest in finding new natural sources of 3'-8″-biflavones and optimizing methods for their extraction and identification. Herein, we have summarized the available data on the structural diversity, natural occurrence, role in plants, extraction, and identification of 3'-8″-biflavones.