Purpose: To evaluate the effect of an acid containing 2% chlorhexidine (Ac/CHX) or a 2% CHX aqueous solution (Aq/CHX) on the immediate and 5-year bonding properties of resin/dentin interfaces produced by two adhesives. The presence of CHX in these interfaces was also evaluated under micro-Raman spectroscopy. Materials and Methods: Forty-two molars were ground to expose a flat dentin surface. In the control group, the surfaces were etched with conventional phosphoric acid, and Prime&Bond NT (PB) and Adper Single Bond 2 (SB) were applied. In Ac/CHX, an acid containing 2% CHX was applied after adhesive application. In the Aq/CHX group, an aqueous solution of 2% CHX was applied for 60 s after etching. After placing the restoration, specimens were prepared and tested using the microtensile bond strength test (μTBS, 0.5 mm/min) immediately or after 5 years. For nanoleakage (NL), specimens at each period were immersed in silver nitrate solution and examined by EDX-SEM. In addition, specimens at each period underwent examination for CHX using micro-Raman spectroscopy. Data were submitted to appropriate statistical analysis (a = 0.05). Results: After 5 years, NL was more pronounced in the control than in the Ac/CHX or Aq/CHX (p 0.001). Significant reductions in the μTBS were observed for all groups; however, they were more pronounced for the control (p 0.001). CHX was still present in the hybrid layers Ac/CHX or Aq/CHX groups after 5 years. Conclusion: The use of a 2% chlorhexidine-containing acid or the application of an aqueous CHX primer may increase the long-term stability of resin/dentin interfaces. Keywords: adhesive systems, chlorhexidine, water sorption, nanoleakage, microtensile bond strength, longevity