Photodetectors displaying an ultraviolet (UV) spectral response window are typically based on wide-bandgap semiconductors that have long been dominated by inorganic materials that suffer from bottlenecks of low flexibility and a limited material family. Here, we synthesized a novel organic small molecule and controlled its crystallization to suppress leakage currents and facilitate separation of the carriers, and the relationship between the nanoscale phase separation morphology and the optoelectrical performance of the photodetectors is disclosed. Our optimized organic photodetector (OPD) presents a UV spectral response window, with superior self-powered responsivities of 45 mA/W (under 250 nm light) and 70 mA/W (under 300 nm light), outperforming the Si photodiode and rivaling other reported UV self-powered photodetectors. Finally, an imaging system was constructed to demonstrate the application potential of the OPD in UV flexible imaging with high-resolution arrays of 400 pixels × 400 pixels (5 μm × 5 μm per pixel), which could work in bent states and successfully output images of micrometer-sized objects.