Abstract The aim was to evaluate the effect of 2% grape seed extract (GSE) containing phosphoric acid (PhA) on the bond strength to enamel and dentin. The control group was 37% PhA. The following three PhA formulations with 2% GSE and 20% ethanol were obtained: GSE5 = 5% PhA; GSE10 = 10% PhA; and GSE20 = 20% PhA. The enamel and dentin surfaces of molars were etched with the acid solutions, followed by Scotchbond Multi-Purpose adhesive and composite resin application. The tensile bond strength (TBS) test evaluated the bond to enamel after 24 h, and the microtensile bond strength (μTBS) test evaluated the bond to dentin after 24 h and 12-month water storage. Etched enamel and dentin were observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. The TBS data were submitted to one-way ANOVA, while µTBS data were submitted to two-way ANOVA and Tukey's test (α = 0.05). The TBS (MPa) to enamel did not significantly differ among the control (48.1 ± 15.7), GSE5 (46.1 ± 9.6), GSE10 (49.8 ± 13.6) and GSE20 (44.1 ± 11.9) groups (p = 0.537). The µTBS (MPa) to dentin of the control (28.4 ± 14.4) and GSE20 (24.1 ± 8.1) groups were significantly higher than those of the GSE5 (16.8 ± 7.4) and GSE10 (17.5 ± 6.6) groups at 24 h (p < 0.006). After 12-month storage, only GSE5 (21.0 ± 7.8) and GSE10 (17.6 ± 8.0) did not show significantly decreased μTBS (p > 0.145). SEM micrographs showed a shallower enamel etching pattern for GSE5. AFM images showed the formation of collagenous globular structures for GSE5 and GSE10. The different acid solutions did not influence the TBS to enamel, and the µTBS to dentin was stable over time when dentin was etched with GSE5 and GSE10.