Five-membered aromatic heterocycles are a ubiquitous skeleton of pi-conjugated organic compounds, and their incorporation requires synthetic protocols that are not easily industrially sustainable or scalable. Improved methodologies for their insertion into pi-scaffolds are therefore necessary. We report an efficient and scalable protocol involving a one-pot cross-Aldol direct arylation reaction protocol for the rapid construction of thiophene- and furan-based pi-extended organic materials.