New pyreno[4,5-b]furan and pyreno[4,5-b:9,10-b']difuran derivatives displaying intense blue fluorescence in CH2Cl2 were efficiently synthesized through the reactions of pyrene-4,5-dione and 2,7-di-tert-butylpyrene-4,5,9,10-tetraone with benzylphosphoranes as a key step. X-ray crystallographic analysis reveals that both pyrenofurans have a planar structure, and their electrochemical properties obviously indicate high HOMO energy levels as predicted by density functional theory (DFT) calculations.