This study reports the synthesis and properties (in particular, the electrical switching characteristics) of a new high-performance polyimide (PI), poly(3,3′-di(4-(diphenylamino)benzylidenyliminoethoxy)-4, 4′-biphenylene hexafluoroisopropylidenediphthalimide) (6F-HAB-TPAIE PI). This PI polymer bears diphenylaminobenzylidenylimine moieties as side groups and is dimensionally stable up to 280 °C and thermally stable up to 440 °C. In devices fabricated with the PI polymer as an active memory layer, the active PI polymer was found to operate at less than (2 V in electrically bistable unipolar and bipolar switching modes by controlling the compliance current. The PI polymer layer exhibits repeatable writing-reading-erasing capability with high reliability in ambient air conditions as well as at high temperatures up to 130 °C. This PI polymer also exhibits a high ON/OFF current ratio up to 109. The observed nonvolatile memory behaviors are due to Schottky emission and local filament formation. This study has demonstrated that this thermally, dimensionally stable PI polymer is a promising material for mass production at low cost for high-performance, programmable, nonvolatile memory devices that can be operated with low power consumption in unipolar and bipolar switching modes.