This study aimed to assess dentin bond durability of 4-META/MMA-TBB resin cement over ten years, by evaluating the tensile bond strength, and SEM and TEM observations. Tensile bond strength of Super Bond C&B (SB) to bovine dentin was evaluated at 1 day and after 10 years. The mode of failure after debonding was observed by SEM. Interfacial ultrastructure and nanoleakage was observed by TEM at the baseline and after 10 y. The tensile bond strength significantly dropped after 10 y. The failure pattern shifted from cohesive failure in resin towards adhesive failure or cohesive failure in dentin. TEM observation revealed degradation of both resin and collagen networks within the hybrid layer and nanoleakage at the base of the hybrid layer after 10 y. The bond strength of SB to dentin significantly decreased, and the hybrid layer degraded, while the overlying hydrophobic resin layer showed little disintegration over 10 y.