Herein, we developed a novel strategy for synthesizing ladder (thio)furan-fused phospholes via intermolecular phosphonation cyclization and a base-promoted phospha-Friedel-Crafts reaction under mild conditions. The starting substrates are readily available phosphinic acids and easy-to-handle alkynes. The details of the reaction mechanism were further rationalized using theoretical calculations. This protocol can be widely applied to synthesize furan- and thiofuran-fused phospholes as well as the corresponding large π-extended derivatives, which are of great interest in the domain of organic functional materials.