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Tomato early blight, caused by <i>Alternaria solani</i>, is a destructive foliar fungal disease. Herein, the potential defensive roles of benzoic acid (BA) and two of its hydroxylated derivatives, <i>ρ</i>-hydroxybenzoic acid (HBA), and protocatechuic acid (PCA) against <i>A. solani</i> were investigated. All tested compounds showed strong dose-dependent fungistatic activity against <i>A. solani</i> and significantly reduced the disease development. Benzoic acid, and its hydroxylated derivatives, enhanced vegetative growth and yield traits. Moreover, BA and its derivatives induce the activation of enzymatic (<i>POX</i>, <i>PPO</i>, <i>CAT</i>, <i>SlAPX</i>s, and <i>SlSODs</i>) and non-enzymatic (phenolics, flavonoids, and carotenoids) antioxidant defense machinery to maintain reactive oxygen species (ROS) homeostasis within infected leaves. Additionally, BA and its hydroxylated derivatives induce the accumulation of salicylic acid (SA) and its biosynthetic genes including isochorismate synthase (<i>SlICS</i>), aldehyde oxidases (<i>SlAO1</i> and <i>SlAO2</i>), and phenylalanine ammonia-lyases (<i>SlPAL1</i>, <i>SlPAL2</i>, <i>SlPAL3</i>, <i>SlPAL5</i>, and <i>SlPAL6</i>). Higher SA levels were associated with upregulation of pathogenesis-related proteins (<i>SlPR-1</i>, <i>SlPR1a2</i>, <i>SlPRB1-2</i>, <i>SlPR4</i>, <i>SlPR5</i>, <i>SlPR6</i>), nonexpressor of pathogenesis-related protein 1 (<i>SlNPR1</i>), and salicylic acid-binding protein (<i>SlSABP2</i>). These findings outline the potential application of BA and its hydroxylated derivatives as a sustainable alternative control strategy for early blight disease and also deciphering the physiological and biochemical mechanisms behind their protective role.