Metal–organic frameworks (MOFs) have recently emerged as a new class of photocatalysts. However, most of these systems suffer from poor visible-light utilization, high cost, and low activity, and photocatalytically active MOFs in the visible-light spectral region are still relatively rare. Herein, a simple and effective strategy was developed to immobilize 2′,7′-dichlorofluorescein inside a porous metal–organic framework (MOF) for the first time. The MOF was applied as the first example of a visible-light responsive MOF-based catalyst for straightforward synthesis of 1,3-oxathiolane-2-imines from styrenes and ammonium thiocyanate under ambient air at room temperature, exhibiting good reusability, and the product can be scaled up to the gram level. The catalytic mechanism was also discussed. The approach reported in this study could open a new avenue in developing novel porous functional materials for a broad scope of visible-light-driven applications.