The development of metal organic framework (MOF)-based self-powered photodetectors is still in its infancy stages, and the device performances still require further improvements. In this study, the Ce-BTC MOF films were first prepared by a spin coating method. By adjusting the spin coating volume of the Ce-BTC solution, the optoelectrical properties of the Ce-BTC films are controlled. The obtained Ce-BTC/n-Si photodetector achieves a commercial-grade responsivity (>100 mA/W), along with exceptional detectivity and ultrafast decay time, surpassing conventional MOF-based counterparts. Moreover, the Ce-BTC/ZnO flexible self-powered photodetector marks a breakthrough, exhibiting superior responsivity (2 mA/W) and detectivity (7.98 × 1010 Jones) that outshine all previously reported MOF-based self-powered photodetectors. This study not only broadens the application prospects of MOF materials in optoelectronics but also provides novel design strategies for flexible multifunctional devices, highlighting the remarkable transformative potential of MOFs as a new class of semiconducting materials.