Numerous studies have focused on the remarkable adhesive properties of polydopamine, which can bind to substrates with a wide range of surface energies, even under aqueous conditions. This behavior suggests that polydopamine may be an attractive option as a surface treatment in structural bonding applications, where good bond durability is required. Here, we assessed polydopamine as a surface treatment for bonding aluminum plates with an epoxy resin. A model epoxy adhesive consisting of diglycidyl ether of bisphenol A (DGEBA) and Jeffamine D230 polyetheramine was employed, and lap shear measurements (ASTM D1002 10) were made (i) under dry conditions to examine initial bond strength and (ii) after exposure to hot/wet (63 °C in water for 14 days) conditions to assess bond durability. Surprisingly, our results showed that polydopamine alone as a surface treatment provided no benefit beyond that obtained by exposing the substrates to an alkaline solution of tris buffer used for the deposition of polydopamine. This implies that polydopamine has a potential Achilles' heel, namely, the formation of a weak boundary layer that was identified using X-ray photoelectron spectroscopy (XPS) of the fractured surfaces. In fact, for longer deposition times (2.5 and 18 h), the tris buffer-treated surface outperformed the polydopamine surface treatments, suggesting that tris buffer plays a unique role in improving adhesive performance even in the absence of polydopamine. We further showed that the use of polydopamine-3-aminopropyltriethoxysilane (APTES) hybrid surface treatments provided significant improvements in bond durability at extended deposition times relative to both polydopamine and an untreated control.