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Abstract Traditional MOF e‐CRR, constructed from catalytic linkers, manifest a kinetic bottleneck during their multi‐electron activation. Decoupling catalysis and charge transport can address such issues. Here, we build two MOF/e‐CRR systems, CoPc@NU‐1000 and TPP(Co)@NU‐1000, by installing cobalt metalated phthalocyanine and tetraphenylporphyrin electrocatalysts within the redox active NU‐1000 MOF. For CoPc@NU‐1000, the e‐CRR responsive Co^I/0potential is close to that of NU‐1000 reduction compared to the TPP(Co)@NU‐1000. Efficient charge delivery, defined by a higher diffusion (D_hop=4.1×10⁻¹² cm² s⁻¹) and low charge‐transport resistance (=59.5 Ω) in CoPC@NU‐1000 led FE_CO=80 %. In contrast, TPP(Co)@NU‐1000 fared a poor FE_CO=24 % (D_hop=1.4×10⁻¹² cm² s⁻¹and=91.4 Ω). For such a decoupling strategy, careful choice of the host framework is critical in pairing up with the underlying electrochemical properties of the catalysts to facilitate the charge delivery for its activation.