Herein, we represent the fabrication of self-biased visible-blind UV photodetector based on thermally deposited N,N′-Bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD) film over n-type silicon substrate giving rise to the structure Au/TPD/n-Si/Al heterojunction. The microelectronic parameters of the fabricated heterojunction Au/TPD/n-Si/Al as well as the charge carriers' transport mechanisms in forward and reverse bias conditions are analyzed and interpreted in detail under the dark conditions and the influence of temperature. The manufactured photodetector showed a significant response to UV illumination with high photocurrents and noticeable values of open-circuit voltage. The fabricated UV photodetector under self-biasing and illumination intensity (100 mW/cm2) records values of responsivity, specific detectivity, linear dynamic range, signal to noise ratio, the response time, and ON/OFF ratio equals 147 mA/W, 6.4 × 1010 Jones, 58.69 dB, 945.5, 82/80 ms, and 861.98, respectively. This high, stable, and fast performance of the fabricated sensor suggest this architecture as an efficient integrated platform for self-biased UV photodetection.