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The scaffold-based drug design has been widely used in new drug discovery. Biphenyl and its analog scaffold are found in many drugs and naturally occurring compounds. To date an array of synthetic methodologies have been introduced to access biphenyl analogs with good yield. Biphenyl scaffolds have shown wide range of biological activities such as anti-inflammatory, antihypertensive, treatment of CNS disorders, anti-cancer, anti-HIV, etc. Also, the importance of biphenyl atropisomers is discussed. This review aims to highlight the evidence of biphenyl motif as a privileged scaffold in various natural products and anticancer agents.