This work reports a highly sensitive self-powered ultraviolet photodetector, which is based on the active layer of NPD:Alq3 with different Alq3 contents. All solution-processed technique was utilized to fabricate the active layers of the devices to achieve an optimized system that exhibits highly sensitive and stable photodetector under self-powered operation mode. The values of photosensitivity, responsivity, and detectivity of the photodiodes at zero-bias were estimated at 1.30 × 105, 1.07 mA/W, 1.04 × 1011 Jones, respectively. The rise and decay times of the optimized device were estimated at 0.34 s and 0.28 s, respectively. For practical application of the device sensing efficiency, the optimal load line of self-powered UV photodetector to deliver the maximum power was estimated of an internal impedence of 0.579 MΩ. In conclusion, the high sensitivity, good stability, and fast response/recovery speed of the self-powered UV photodetector make the devices applicable to resolve some of the current issues in UV detection.