The isolation and structural characterization of a unique Cu(II) isonicotinate (ina) material with 4-acetylpyridine (4-acpy) is provided. The formation of [Cu(ina)2(4-acpy)]n(1) is triggered by the Cu(II) aerobic oxidation of 4-acpy using O2. This gradual formation of ina led to its restrained incorporation and hindered the full displacement of 4-acpy. As a result,1is the first example of a 2D layer assembled by an ina ligand capped by a monodentate pyridine ligand. The Cu(II)-mediated aerobic oxidation with O2was previously demonstrated for aryl methyl ketones, but we extend the applicability of this methodology to heteroaromatic rings, which has not been tested so far. The formation of ina has been identified by1H NMR, thus demonstrating the feasible but strained formation of ina from 4-acpy in the mild conditions from which1was obtained.