A modular synthetic methodology has been developed to prepare β-diketones functionalized with hole- and electron-transporting fragments at their two termini. The optical and electrochemical properties of these new β-diketones are also described in detail.A modular synthetic methodology has been developed to prepare β-diketones functionalized with hole- and electron-transporting fragments at their two termini. The optical and electrochemical properties of these new β-diketones are also described in detail.