Soil salinization is a major threat to agricultural sustainability. Poly-gamma-glutamic acid (γ-PGA), a biopolymer produced by microbial fermentation, has received attention as a biostimulant due to its positive effects on crop performance. However, the function of γ-PGA in crop salt stress tolerance and its effect on the rhizosphere are unclear. This study explores the effects of γ-PGA application on rhizosphere soil nutrients and the soil–physical environment and examines the salt tolerance response of maize seedlings grown in saline–alkali soil under such an application regime. The results show a significant promotion of maize seedling growth and of nutrient accumulation with γ-PGA application under salt stress; plant dry weight, stem diameter, and plant height increased 121%, 39.5%, 18.4%, respectively, and shoot accumulation of nitrogen, phosphorus, potassium, and carbon increased by 1.38, 2.11, 1.50, and 1.36 times, respectively, under an optimal-concentration γ-PGA treatment (5.34 mg kg⁻¹ (12 kg ha⁻¹)) compared with the control. γ-PGA treatment significantly decreased rhizospheric pH and soil electrical conductivity and significantly increased nutrient availability in the rhizosphere, especially available nitrogen (AN) and available potassium (AK). Compared with the control, AN, available phosphorus (AP), and AK increased by 13.9%, 7.70%, and 17.7%, respectively, under an optimal concentration treatment with γ-PGA. γ-PGA application also significantly increased the activities of urease, acid phosphatase, alkaline phosphatase, dehydrogenase, and cellulose in rhizosphere soil by 35.5–39.3%, 35.4–39.3%, 5.59–8.85%, 18.9–19.8%, and 19.2–47.0%, respectively. γ-PGA application significantly decreased Na⁺ concentration and increased K⁺ concentration in shoots, resulting in a lowering of the Na⁺/K⁺ ratio by 30.5% and an increase in soluble sugar and soluble protein contents. Therefore, rhizosphere application of water-soluble and biodegradable γ-PGA facilitates the creation of an optimized rhizospheric environment for maize seedling and overcomes osmotic and ionic stresses, offering possibilities for future use in drip-irrigation systems in the cultivation of crops on saline-alkali land.