The mechanism of phosphate (Pi)-mediated salt tolerance in maize is poorly understood. In this study, the effects of Pi (H2PO4-) on the salt tolerance of two contrasting genotypes was investigated in a pot experiment. We discovered that the application of 3 mM Pi could alleviate salt injury caused by 200 mM NaCl. High amounts of compatible solutes and low amounts of reactive oxygen species (ROS) were also observed under Pi application. Consistent with the increased tolerance, the total number of roots and the growth of shoots increased to relieve salt stress. This phenomenon could be associated with the observed increased expression of nitrate transporters. Furthermore, the seedlings presented a negative relationship between sodium (Na+) and Pi (low Na+ content and high Pi content), which is related to the genes ZmNHX1, ZmPHT1;8, and ZmPHT1;9, indicating that the exclusion of Na+ was promoted by high Pi uptake. However, high Na+ and low potassium (K+) efflux were detected in the roots, and these were positively correlated with two K+ transporters. These observations indicate that Na+ exclusion was directly induced by high K+ retention rather than Pi absorption. We conclude that maize salt tolerance increased in response to Pi application by promoting Na+ exclusion.