Silicon (Si) has been well documented to alleviate aluminum (Al) toxicity in vascular plants. However, the mechanisms underlying these responses remain poorly understood. Here, we assessed the effect of Si on the modulation of Si/Al uptake and the antioxidant performance of ryegrass plants hydroponically cultivated with Al (0 and 0.2 mM) in combination with Si (0, 0.5, and 2.0 mM). Exposure to Al significantly increased Al concentration, mainly in the roots, with a consequent reduction in root growth. However, Si applied to the culture media steadily diminished the Al concentration in ryegrass, which was accompanied by an enhancement in root dry matter production. A reduced concentration of Si in plant tissues was also observed when plants were simultaneously supplied with Al and Si. Interestingly, Si transporter genes (Lsi1 and Lsi2) were down-regulated in roots after Si or Al was applied alone; however, both Lsi1 and Lsi2 were up-regulated as a consequence of Si application to Al-treated plants, denoting that there is an increase in Si requirement in order to cope with Al stress in ryegrass. Whereas Al addition triggered lipid peroxidation, Si contributed to an attenuation of Al-induced oxidative stress by increasing phenols concentration and modulating the activities of superoxide dismutase (SOD), catalase, peroxidase, and ascorbate peroxidase antioxidant enzymes. Differential changes in gene expression of SOD isoforms (Mn-SOD, Cu/Zn-SOD, and Fe-SOD) and the profile of peroxide (H2O2) generation were also induced by Si in Al-stressed plants. This, to the best of our knowledge, is the first study to present biochemical and molecular evidence supporting the effect of Si on the alleviation of Al toxicity in ryegrass plants.