Direct 2C-ring expansion of 1-indanones with ynones to 5H-benzo[7]annulenes has been observed, and its generality has been gauged (19 examples). Overall, this simple and convenient cascade process to 5H-benzo[7]annulenes involves engagement of 1-indanone with two ynone moieties with formation of three new C-C σ-bonds, cleavage of C-C σ-bond, and concurrent functionality amplification. The resulting seven-membered ring, laced with an opportunistic disposition of four proximal functional groups, offers avenues for their further productive interplay. Our new approach embraces many green and eco-friendly features.