It has been reported that fulvic acid (FA) application improves soil structure and nutrient availability. However, the effects of combined application of urea (U) and FA solution on the photosynthesis and nitrogen metabolism in maize (Zea mays L.) have rarely been reported. In this study, pot experiments were conducted in 2017 and 2018, and the effects of combined application of urea and FA solution (U+FA) on soil available nutrient contents, maize endogenous hormone concentrations, carbon and nitrogen metabolism-related enzyme concentrations, maize yield, and nitrogen use efficiency (NUE) were researched. Compared with the U treatment, the maize yield and NUE in the U+FA treatment were significantly increased by 8.31% and 17.09 percentage points in 2017 and by 16.90% and 24.31 percentage points in 2018. At the jointing and 12-leaf (V12) stages of maize, soil NH4+ content increased by 139.32% and 12.08%, separately, in the U+FA treatment. At the V12 stage, the auxin, nitrate reductase, nitrite reductase, and glutamine synthetase concentrations in maize root were increased by 42.31%, 74.17%, 16.61%, and 45.60%, respectively, and the concentrations of pyruvate phosphate dikinase and phosphoenolpyruvate carboxylase in maize leave were increased by 29.40% and 42.96%, respectively, in the U+FA treatment. The combined application of urea and FA solution significantly improved soil nutrient availability, increased the concentrations of endogenous hormones in maize, stimulated the activities of enzymes related to nitrogen metabolism, promoted the photosynthetic carbon assimilation efficiency, and ultimately improved crop yield and NUE.