This article describes the generalization of an overlooked mechanism for CH bond activation at early transition metal centers, namely 1,3‑CH bond addition at an η²-alkene intermediate. The X-ray-characterized [Cp₂Zr­(c-C₃H₅)₂] eliminates cyclo­propane by a β‑H abstraction reaction to generate the transient η²-cyclo­propene [Cp₂Zr­(η²-c-C₃H₄)] intermediate A. A rapidly cleaves the CH bond of furan and thiophene to give the furyl and thienyl complexes [Cp₂Zr­(c-C₃H₅)­(2-C₄H₃X)] (X = O, S), respectively. Benzene is less cleanly activated. Mechanistic investigations including kinetic studies, isotope labeling, and DFT computation of the reaction profile all confirm that rapid stereo­specific 1,3‑CH bond addition across the Zr­(η²-alkene) bond of A follows the rate-determining β‑H abstraction reaction. DFT computations also suggest that an α‑CC agostic rotamer of [Cp₂Zr­(c-C₃H₅)₂] assists the β‑H abstraction of cyclo­propane. The nature of the α‑CC agostic interaction is discussed in the light of an NBO analysis.