Abstract In this paper, the photophysical properties of a hybrid material, composed of a conjugated polymer and perovskite nanocrystals, are investigated by ultrafast spectroscopy and morphological characterization. The relaxation dynamics of a drop‐casted film from the semiconducting polythiophene (P3HT) and a green‐emitting CsPbBr 3 (zwitterionic sulfobetaine ‐capped) perovskite nanocrystals (NCs) solution is studied. The transient spectroscopy presents a very long photobleaching signal peaked at 516 nm not present in the single components of the blend. The scanning electron and confocal fluorescence microscopy images show that the P3HT and the CsPbBr 3 NCs are finely mixed in the film. The presence of a very efficient hole transfer from the nanocrystal to the polymeric chain that induces the formation of a long ‐lived charge‐transfer state as shown in the pump‐probe measurements is proposed. The theoretical model reveals the important role of the zwitterionic sulfobetaine capper in this process. The perovskite strongly adsorbs the surfactant, while the polythiophene chain is not directly bound to the perovskite. Instead, it interacts with the surfactant itself, contributing to the electronic properties of the overall system.