Silicon (Si) exerts beneficial effects in mitigating aluminum (Al) toxicity in different plant species. These include attenuating oxidative damage and improving structural strengthening as a result of the increased production of secondary metabolites such as phenols. The aim of this research was to evaluate the effect of Si on phenol production and composition in two barley cultivars under Al stress. Our conceptual approach included a hydroponic experiment with an Al-tolerant (Sebastian) and an Al-sensitive (Scarlett) barley cultivar treated with two Al doses (0 or 0.2 mM of Al) and two Si doses (0 or 2 mM) for 21 days. Chemical, biochemical and growth parameters were assayed after harvest. Our results indicated that the Al and Si concentration decreased in both cultivars when Al and Si were added in combination. Silicon increased the antioxidant activity and soluble phenol concentration, but reduced lipid peroxidation irrespective of the Al dose. Both barley cultivars showed changes in culm creep rate, flavonoids and flavones concentration, lignin accumulation and altered lignin composition in Si and Al treatments. We concluded that Si fertilization could increase the resistance of barley to Al toxicity by regulating the metabolism of phenolic compounds with antioxidant and structural functions.