The photocycloaddition reaction of benzene with alkenes has become a significant approach for organic chemists and thus has been frequently utilized as a key step in the total synthesis of natural products. In this mini-review, the recent developments in [4 + 2] and [2 + 2] photocycloaddition reactions will be emphasized in constructing core scaffolds of complex natural products. By combining them together, we aim to demonstrate the utility and reinstate the importance of this methodology.