The study was conducted to evaluate the influence of silicon application on the botanical composition of grass–legume mixtures as well as the nutritional value of individual species and mixtures. The two-factor field experiment was established in a split-block arrangement. The two grass–legume mixtures, consisting of Dactylis glomerata, Festulolium braunii and Trifolium pratense or Medicago x varia and grass mixture—Dactylis glomerata, Festulolium braunii and Lolium perenne, were sown on arable land. Silicon foliar and mineral NPK fertilization was applied in three variants: NPK (non-Si-fertilized), NPK+Si (Herbagreen), NPK+Si (Optysil). Changes in the botanical composition in the sward of mixtures during the study period were influenced by the competitiveness of individual plants and weather conditions, whereas the effect of foliar fertilization with silicon was only slightly marked. The nutritional value of individual species of grasses and legumes varied over the years and also depended on the application of silicon. The greatest content of crude protein (CP), irrespective of the species and variant of silicon fertilization, was noticed in years with no drought. Our research confirmed the beneficial effect of silicon fertilization, independent of weather conditions, on the CP content and on the reduction of crude fibre (CF), neutral detergent fibre (NDF) and acid detergent fibre (ADF) in plants, especially when Herbagreen was applied. The nutritional value of the mixtures under applied silicon fertilization depended on botanical composition. In the conditions of low rainfall, a large share of F. braunii and an approximately 20% contribution of T. pratense resulted in a higher content of CP. These results may be used in the fertilization practices of temporary grassland for enhancing nutritional value, especially crude protein content, and on the reduction of fibre in the sward.