Objectives: Zinc-doped dentine adhesives have been recently advocated to interfere with metallo-proteinases-mediated collagen degradation. Nevertheless, there is a little information about the effects of zinc ions on the chemical interaction of self-etch functional monomers to dentine. The aim of this study was to assess if the inclusion of zinc into the primers of self-etch adhesives containing MDP (10-methacryloyloxi-decyl-dihydrogen-phosphate) may interfere with their chemical interaction to calcium/dentine. Methods: Caries-free human molars were bonded using two commercial self-etching adhesives [Clearfil SE bond (CSE) and S3 bond (S3)] doped with zinc nitrate and submitted to microtensile bond strength (μTBS) and interface nanoleakage evaluation. Moreover, MDP was synthesised to evaluate the chemical interaction with calcium/dentine through atomic absorption spectroscopy (AAS) and SEM-EDX in the presence or absence of zinc ions. Results: AAS showed increasing formation of MDP-zinc rather than MDP-calcium salts (p = 0.002) in the presence of zinc. SEM-EDX confirmed the formation of zinc-rich phosphate deposits that were probably responsible for the significant reduction in μTBS and increased interfacial nanoleakage attained with zinc-doped CSE and S3. Conclusion: These outcomes demonstrated that the excessive presence of zinc ions may jeopardise the bonding performance of MDP-containing self-etch adhesives. © 2014 Elsevier Ltd. All rights reserved.