A series of D–π–A star-shaped molecules has been investigated theoretically by using density functional theory (DFT) to reveal their optical, electronic, and charge transport properties for applications in organic light-emitting diodes (OLEDs) and organic solar cells (OSCs). The calculated results show that their optical, electronic, and charge transport properties are affected by the different end groups and π-bridges. Our results reveal that the molecules under investigation can serve as OSCs donor materials and/or luminescent materials for OLEDs. In addition, all molecules are expected to be promising candidates for hole- and electron-transport materials. On the basis of the obtained results, we propose a rational way for the design of multifunctional materials for OLEDs and OSCs applications.