The functionalization of polycyclic aromatic hydrocarbons (PAHs) with arynes has received substantial attention because it offers a way to create pi-extended PAHs as well as compounds containing rigid 3D structures. Herein, we report cycloadditions of benzyne to a pi-extended tetracene with a twisted framework. Under kinetic control, this reaction furnished mono-and bisadducts via concerted [4+2] cycloadditions, which was supported by theoretical studies. The bisadduct exhibits blue emission in the solid state on account of the steric protection arising from the two [2.2.2] bicyclic moieties.