An efficient synthetic approach to construct a fully substituted benzo[1,2-b:4,5-b']difuran (BDF) 2a via base-catalyzed double annulations is presented. Compound 2a can readily undergo Suzuki, Heck, and Sonogashira coupling reactions to afford in good yields a manifold of extended pi-conjugated BDF derivatives, e.g., with pyridine termini (4-6) and with different spacers. These are highly luminescent materials that undergo two reversible one-electron oxidations. Remarkably, their photophysical and electrochemical properties can be largely tuned by methylation or protonation. Consequently, they can function as pH-dependent fluorescence switches. Finally, the observed electronic properties are explained on the basis of density functional theory.