Six new triterpenoids (1–6), two known genins (7 and 8), and five known functionalized triterpenoids (9–13) were isolated from a Quercus robur heartwood extract. The purification protocol was guided by LC-HRMS by searching for structural analogues of bartogenic acid on the basis of their putative empirical formula. The structures of the new compounds were unequivocally elucidated using HRESIMS and 1D/2D NMR experiments. Sensory analyses were performed in water and in a non-oaked white wine on the pure compounds 1–13 at 5 mg/L. All molecules were perceived as bitter in water and wine, but they were mostly reported as modifying the wine taste balance. Using LC-HRMS, compounds 1–13 were observed in oaked red wine and cognac and were semiquantified in oak wood extracts. The influence of two cooperage parameters, oak species and toasting process, on compounds 1–13 content was studied. All compounds were found in quantities significantly higher in pedunculate than in sessile oak wood. Toasting is a key step in barrel manufacture and modulates the concentration of the discussed compounds. Significantly higher quantities were observed in untoasted wood compared to medium or highly toasted wood. These findings provide new insights into the molecular origin of taste changes due to oak aging.Read less <