A series of aromatic polyimides (PIs) were synthesized via the polymerization of 3,3prime;,4,4′-diphenylsulfonyltetracarboxylic dianhydride with 4,4′-diaminotriphenylamine derivatives containing hydrogen, cyano, methoxy, or dimethylamine substituents. These PIs were thermally and dimensionally stable and produced high-quality thin films when applied in a conventional spin-coating process. Their structure and properties were characterized. Nanoscale thin films of the PIs demonstrated excellent electrical memory performance, with high stabilities and ON/OFF current ratios. The memory characteristics were found to be tunable by varying the substituents; nonvolatile write-once-read-many-times memory behavior, nonvolatile ON/OFF switching type memory behavior, and volatile dynamic random access memory behavior were observed. The memory characteristics were substantially influenced by the electron-accepting cyano- and electron-donating dimethylamine substituents but were apparently not affected by the electron-donating methoxy substituent. In addition, the film density was a significant factor influencing the observed memory behaviors, with larger film densities causing lower OFF-current levels. However, the critical switching-on voltage varied very little as the substituents were changed and was measured to be approximately 2 V. All of the memory behaviors were found to be governed by a mechanism involving trap-limited space-charge-limited conduction and local filament formation. Overall, all of the PIs assessed in the present work were found to be suitable active materials for the low-cost mass production of high-performance, programmable unipolar memory devices that can be operated with very low power consumption, high ON/OFF current ratios, and high thermal and dimensional stability.