A series of brush copolymers bearing N-phenylcarbazole (PK) and 2-biphenyl-5-(4-ethoxyphenyl)-1,3,4-oxadiazole (BEOXD) moieties in various compositions were studied in detail, in particular their electrical memory characteristics, optical and electrical properties, morphological structures, and interfaces. Nanoscale thin films of the brush copolymers in devices were found to exhibit excellent unipolar electrical memory versatility, which can easily be tuned by tailoring the chemical composition and by changing the film thickness. Moreover, the molecular orbitals and band gap can be tuned by changing the chemical composition. The novel memory characteristics of these copolymers originate primarily from the cooperative roles of the ambipolar PK and BEOXD moieties, which have different charge trapping and stabilization properties. The electrical memory behaviors were found to occur via a favorable hole injection from the electrode and to be governed by trap-limited space-charge limited conduction combined with ohmic conduction and local filament formation. Overall, the brush copolymers are very suitable active materials for the low-cost mass production of high performance, polarity-free digital memory devices that can be operated with very low power consumption, high ON/OFF current ratios, and high stability.