Electron donor–acceptor triblock and diblock copolymers have attracted considerable interest due to their potential applications in all-polymer solar cells as single-active components or surfactants. However, the number of donor–acceptor block copolymers has lagged behind that of the rod–coil and rod–rod block copolymers due to their synthetic difficulties. This minireview highlights the recent advances in the synthetic strategies for the all-conjugated donor–acceptor block copolymers and their application in all-polymer solar cells.

Neuromorphic computation possesses the advantages of self‐learning, highly parallel computation, and low energy consumption, and is of great promise to overcome the bottleneck of von Neumann computation. In this work, a series of poly(3‐hexylthiophene) (P3HT)‐based block copolymers (BCPs) with different coil segments, including polystyrene, poly(2‐vinylpyridine) (P2VP), poly(2‐vinylnaphthalene), and poly(butyl acrylate), are utilized in photosynaptic transistor to emulate paired‐pulse facilitation, spike time/rate‐dependent plasticity, short/long‐term neuroplasticity, and learning−forgetting−relearning processes. P3HT serves as a carrier transport channel and a photogate, while the insulating coils with electrophilic groups are for charge trapping and preservation. Three main factors are unveiled to govern the properties of these P3HT‐based BCPs: i) rigidity of the insulating coil, ii) energy levels between the constituent polymers, and iii) electrophilicity of the insulating coil. Accordingly, P3HT‐b‐P2VP‐based photosynaptic transistor with a sought‐after BCP combination demonstrates long‐term memory behavior with current contrast up to 10⁵, short‐term memory behavior with high paired‐pulse facilitation ratio of 1.38, and an ultralow energy consumption of 0.56 fJ at an operating voltage of −0.0003 V. As far as it is known, this is the first work to utilize conjugated BCPs in an electret‐free photosynaptic transistor showing great potential to the artificial intelligence technology.