The homogeneous system demonstrates limited reusability under the industrial mixture conditions, and the catalytic solution stops working after three re-uses. To increase recyclability and to improve the durability of our system, we translated our homogeneous system into a heterogeneous one by incorporating molecular cobaloxime as linkers in a MOF. Our heterogeneous system displays similarly fast reduction kinetics and excellent selectivity for acetylene semihydrogenation as the homogeneous system. Critically, the MOF-based system retains catalytic activity for more than twice as long as the homogeneous system (48 hours of irradiation) and can be recycled twice as many times before performance deteriorates. The photocatalytic semi-hydrogenation of C2H2 using cobaloxime-based photocatalytic systems can be achieved using either (b) a homogeneous molecular approach or a heterogeneous MOF-based approach (structural model as reported ).