Organic molecules with donor-acceptor (D-A) structure are an important type of material for nanoelectronics and molecular electronics. The influence of the electron donor and acceptor units on the electrical function of materials is a worthy topic for the development of high-performance data storage. In this work, the effect of different D-A structures (namely D-pi-A-pi-D and A-pi-D-pi-A) on the electronic switching properties of triphenylamine-based molecules is investigated. Devices based on D-pi-A-pi-D molecules exhibit excellent write-read-erase characteristics with a high ON/OFF ratio of up to 10(6), while that based on A-pi-D-pi-A molecules exhibit irreversible switching behavior with an ON/OFF ratio of about (3.2 x 10(1))-(1 x 10(3)). Moreover, long retention time of the high conductance state and low threshold voltage are observed for the D-A switching materials. Accordingly, stable and reliable nanoscale data storage is achieved on the thin films of the D-A molecules by scanning tunneling microscopy. The influence of the arrangement of the D and A within the molecular backbone disclosed in this study will be of significance for improving the electronic switching properties (ON/OFF current ratio and reversibility) of new molecular systems, so as to achieve more efficient data storage through appropriate design strategies.