A new metal‐free synthetic approach to functionalized indenes is documented. The use of commercially available graphene oxide (GO) allowed the direct access to indenyl cores (yield up to 80%) via intramolecular Friedel‐Crafts‐type allylic alkylations with readily available Morita‐Baylis‐Hillman alcohols. Combined experimental and spectroscopic investigations contributed to shed light on the reaction mechanism dealing with a nanostructured carbon material‐based C‐C bond forming reaction.