Metal–Organic Decomposition Ink‐Derived Cu Foams Enable High Formate Selectivity and Methanol Conversion

High‐surface‐area electrodes are required to sustain industrially relevant current densities during selective methanol oxidation to formate. Here, particle‐free Cu metal–organic decomposition (MOD) inks based on Cu(II) formate tetrahydrate and monoisopropanolamine are repurposed as solution‐derived precursor coatings for porous Cu foams. Dip coating under ultrasonication and low‐temperature calcination generate granular Cu structures on the foam surface and in the examined cross‐sectional regions. The resulting MOD Cu foams exhibit substantially increased apparent mass‐normalized double‐layer capacitance and reconstruct under anodic operation into Cu(II)‐rich interfaces with electrochemical behavior consistent with transient formation of Cu(III)‐containing species. In zero‐gap flow‐cell methanol oxidation, the best‐performing MOD(1:1.5) Cu foam reached a maximum formate Faradaic efficiency of 93.9% at 10% methanol conversion and a final methanol conversion of 72.2%, outperforming untreated Cu foam in both selectivity and conversion. These results establish MOD inks as a scalable route to structured Cu electrodes for selective liquid‐phase electrosynthesis.