Abstract Background and Aims While nitrogen (N) supply can enhance plant silicon (Si) accumulation, the mechanisms by which different forms of N affect Si mobilization in the rhizosphere are not well understood. This study aims to elucidate how pH changes induced by ammonium (NH4+) and nitrate (NO3−) affect Si availability in the rhizosphere, especially under low phosphorus (P) conditions. Methods White lupin (Lupinus albus) plants were grown in non-fertilized low-P soil, supplied with a low dose of N, either as NH4+ or NO3−, with or without supply of monosilicic acid. We measured Si levels in various rhizosphere soil pools, along with different plant and rhizosphere soil parameters. Results The addition of NH4+ significantly lowered rhizosphere pH and decreased both Si adsorbed to pedogenic Fe/Mn oxides and amorphous phytogenic Si, resulting in higher concentrations of plant available Si in the white lupin rhizosphere. This led to greater Si uptake and improved plant growth compared to both the –N and + NO3− treatments. The supply of Si further enhanced these effects, with NH4+ showing a consistently different pattern of influence compared to NO3−. Additionally, –N white lupin plants accumulated more P than those treated with N, while Si supply significantly improved P acquisition across all treatments. Conclusions Our study demonstrates that rhizosphere acidification induced by NH4+ nutrition can significantly enhance Si mobilization from the rhizosphere soil in the absence of Si supply and reduce Si adsorption when Si is applied. These findings may have practical implications for improving both Si mobilization in the rhizosphere and the effectiveness of Si fertilizers.