A transition metal‐free approach was developed to achieve substituted furocoumarins via an iodine‐promoted one‐pot cyclization between 4‐hydroxycoumarins and acetophenones. High yields of furocoumarins were achieved in the presence of NH4OAc as an additive, while neither acidic nor basic additives were effective. The reaction would proceed via a 5‐exo‐tet cyclization but not an O‐alkylation. The fact that commercially available starting materials could be used without the need of a transition metal catalyst could be a significant advantage.