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Epoxy to copper adhesion supports the reliability of numerous structures in electronic packaging. Compared to substrate pre‐treatment, processing and cost considerations are in favor of adhesion promoters loaded in epoxy formulations. In this work, first row transition metal β‐diketonates present such a compelling case when added in epoxy/anhydride resins: over 30% (before moisture aging) and 50% (after moisture aging) enhancement in lap shear strength are found using Co(II) and Ni(II) hexafluoroacetylacetonate. From extensive X‐ray photoelectron spectroscopy (XPS) analyses on the adhesively failed sample surfaces, increased population of oxygen‐containing functional groups, especially esters, is linked to the adhesion improvement. Assisted by XPS depth profile on the fractured epoxy side and in situ Fourier‐transform infrared spectroscopy (FTIR), the previously discovered latent cure characteristics endowed by the metal chelates interacting with phosphine catalysts are regarded pivotal for pacing the anhydride consumption and allowing interfacial esterification reactions to occur. Further examinations on the XPS binding energy shifts and dielectric properties of the doped epoxy also reveal metal–polymer coordination that contribute to the adhesion and moisture resistance properties. These findings should stimulate future research of functional additives targeting at cure kinetics control and polar group coordination ideas for more robust epoxy–Cu joints. [ABSTRACT FROM AUTHOR]