Boron (B) is a micronutrient crucial for the growth, development, productivity, and quality of crops. However, in areas characterized by acid soil (pHwater < 5.0) and high rainfall, soil B concentration tends to decrease, leading to insufficient supply to crops. This study was aimed at determining the optimal rate of B fertilization to enhance Vaccinium corymbosum L. performance in acid conditions. One-year-old cultivars with contrasting Al resistance (Al-sensitive Star and Al-resistant Cargo) were used. Plants were conditioned in plastic pots containing 18 L of half-ionic-strength Hoagland solution (pH 4.5) for 2 weeks. Thereafter, the following B treatments were applied foliarly: control, without B application (distilled water), 200, 400, and 800 mg L−1 of B as Solubor® for up to 72 h. Photosynthetic performance, root and shoot B levels, antioxidants, and oxidative stress were evaluated. Root and shoot B concentrations increased with the increasing B application, being higher in leaves than in roots of both cultivars. Net photosynthesis decreased at 800 mg L−1 B supply and effective quantum yield of PSII at 72 h in all B treatments. Lipid peroxidation increased in both cultivars at 800 mg L−1 B treatment. Antioxidant activity increased in all B treatments in both cultivars; while, at 400 and 800 mg L−1 B, total phenols increased in leaves of cultivar Star and decreased in cultivar Cargo. In conclusion, optimal B foliar application for highbush blueberry appears to be around 400 mg L−1 B. The appropriate B foliar application could help mitigate potential stress-induced problems in highbush blueberry cultivation. However, the optimal foliar B application should be confirmed in field experiments to help the farmers manage B nutrition.