Nano-engineered structured boiling surfaces have shown great promise in the improvement of heat dissipation performance in thermal management applications. Electrodeposited copper foams have attracted lots of scientific and engineering interest owing to their multi-tier structures. In this study, hierarchical copper foams with ultra-wicking properties were fabricated using cathodic deposition at different pH, including both acidic (pH 0) and basic (pH 10 and 12) solutions. Pendant droplet wicking tests and pool boiling experiments were performed to characterize the wicking flux and the critical heat flux (CHF) of the fabricated copper foams, respectively. The results show that base deposited copper foams (pH 10 and 12) yield higher wicking flux and higher boiling CHF than acid deposited copper foam (pH 0) due to smaller dendrites and crystallites. The effect of the surface structures on bubble dynamics is probed by analyzing the maximum bubble size, bubble count, and the power and dominant frequency of vapor fraction at varying heat fluxes from high-speed videos. The results reveal no significant differences between tested surfaces (flat copper and copper foams deposited at pH 0, 10, and 12) when the heat flux is kept the same. On the other hand, acoustic emissions (AE) are used to characterize the copper foam structures in both wicking and boiling tests. The results show consistent acoustic signatures between wicking and boiling that smaller AE amplitude is observed for higher wicking flux and higher CHF. Combing the optical and acoustic analysis, it is concluded that the main role of surface structures play in CHF enhancement is through improving capillary wicking underneath the bubbles rather than affecting the dynamics of the apparent liquid-vapor interfaces. This study not only explores the relationship between electrochemical control and wicking properties but also demonstrates the role of wicking in structure-enhanced boiling CHF through acoustic emission analysis.