‘Xinomavro’ (the second planted red Greek variety behind ‘Agiorgitiko’) generally produces wines that are light in colour but with increased astringency, possibly related to grape flavonoid amount and composition; although irrigation is accepted as an effective means to enhance grape phenolic maturity, its role has not yet been sufficiently studied in the case of Xinomavro. This study aimed to determine the effect of post-veraison irrigation on berry anthocyanin and proanthocyanidin amount and composition, of field-grown Xinomavro vines (Vitis vinifera L.), under the typical summer conditions of Northern Greece. In a 10-year-old Xinomavro vineyard, two post-veraison watering regimes were applied—irrigation starting 20 days after veraison (mid-ripening irrigation, MRI) and irrigation starting immediately after veraison was completed (after veraison irrigation, AVI)—alongside non irrigated vines (NI), and vines irrigated continuously from berry set through harvest (continuous irrigation, CI). Proanthocyanidin composition was determined in both skins and seeds by employing phloroglucinolysis followed by HPLC-UV and MS detection (high-performance liquid chromatographic with tandem mass spectrometric and ultraviolet absorbance detection), and the anthocyanin profile was identified only in the skin extracts by HPLC-UV (high-performance liquid chromatographic with ultraviolet absorbance detection). Post-veraison irrigation increased yield parameters and reduced anthocyanin levels and the proportion of their stable forms (acylated vs. non-acylated, tri-oxygenated and methoxylated on the B-ring vs. di-oxygenated and hydroxylated), compared to NI vines; however, these effects were more pronounced in the case of early post-veraison irrigation (AVI) than late-season irrigation (MRI). Irrigation also increased the mean Degree of Polymerization (mDP) and prodelphinidin percentage of skin tannins and decreased mDP of seed tannins. In the light of the necessity to control the accelerated ripening under the increasingly hotter and drier climatic conditions, late irrigation (MRI) might provide a solution to avoid excessive sugar levels and allow a slightly higher yield without significant reductions in berry phenolic content. The results suggest that the optimisation of the timing of irrigation could provide an effective adaptation strategy to climate change in Mediterranean viticultural areas.