Dentin bonded with one-step self-etch adhesives does not couple well to chemically-cured composites despite the presence of ternary catalysts in some systems. To determine whether additional factors are responsible for the poor coupling of dentin bonded with these adhesives, the authors used a one-step self-adhesive in which the ternary catalyst is incorporated separately in the brush applicator for activating the adhesive. The activated adhesive was bonded to dentin or prepolymerized composites. For microtensile bond strength evaluation, a dual-cured hybrid composite was used for coupling to the bonded substrates and activated using: (1) the light-cured mode (LC), (2) delayed light-activation (DL) and (3) the chemical-cured mode (CC). In addition, the composite polymerized in the CC mode was coupled to the two substrates bonded with (4) additional experimental adhesive versions without the ternary catalyst and (5) without the ternary catalyst and tertiary amine. Silver tracer penetration into bonded interfaces was examined using TEM by replacing the dual-cured composite with a light-cured or a chemically-cured microfilled composite. In the CC mode, the composites coupled poorly to both substrates bonded with the unactivated adhesive (5). The use of activated adhesives allowed for good coupling of the composites polymerized in all curing modes to bonded composite, but only in the LC mode to bonded dentin. Water-filled channels in the form of water trees and water blisters were present in the adhesive layer under all composite-curing modes in bonded dentin. These features were completely absent in the bonded composites, showing that the source of the water was from dentin. Water blisters were also observed along the adhesive-composite interfaces in bonded dentin when the coupling composites were polymerized using the CC or DL modes.