The vibration-based electret generators (EGs) for energy harvesting have been extensively studied because they can obtain electrical energy from ambient vibrations. EGs exhibit a sandwich structure of electrodes surrounding an air gap and an electret, which is a dielectric material with a quasi-permanent electrical charge or dipole polarisation. Various charging processes have been developed because the surface charge density (σ) of the electret determines the output power of the device. However, such processes are considered to constitute a key productivity-limiting factor from the mass production viewpoint, making their simplification or elimination a highly desired objective. Herein, a model EG that does not require any charging process by utilising the spontaneous orientation polarisation of 1,3,5-tris(1-phenyl-1H-benzimidazole-2-yl)benzene (TPBi) is demonstrated. The surface potential (V ) of an evaporated TPBi film has reached 30.2 V at a film thickness of 500 nm without using a charging process. The estimated σ of 1.7 mC m is comparable with that obtained using a conventional polymer-based electret after charging. Furthermore, V is considerably stable in environmental conditions; thus, TPBi can be considered to be "self-assembled" electret (SAE). Application of SAE leads to developing an EG without requiring the charging process.