In a wheat/maize rotation system, nitrogen (N) accounts for a large proportion of basal fertilizer, but soil N loss and the resulting environmental risk simultaneously exist worldwide. This study applied different urease/nitrification inhibitors together with basal fertilizers and investigated their effects on soil N level and grain yield. Six N stabilizing combinations consisted of two urease inhibitors (HQ and NBPT) and three nitrification inhibitors (DCD, DMPP, and Nitrapyrin). The treatments supplied with urease/nitrification inhibitors reduced, to some degree, the conversion rate of ${\mathsf{N}\mathsf{H}}_4^{+}$ into ${\mathsf{N}\mathsf{O}}_3^{-}$, and kept ${\mathsf{N}\mathsf{H}}_4^{+}$ content higher in surface soils for a longer time. Compared to CK, A1 treatment supplied with 1.5% HQ + 4% DCD well-maintained the levels of soil alkali-hydrolyzable N and ${\mathsf{N}\mathsf{H}}_4^{+}$. For example, alkali-hydrolyzable N and ${\mathsf{N}\mathsf{H}}_4^{+}$ contents at 0–20 cm soil layer under A1 were increased by 8.59–41.6% and 8.15–14.5% more than CK, respectively. Based on the entire growth period of wheat and maize rotation, urease/nitrification inhibitors improved soil available N in surface soils but did not prevent ${\mathsf{N}\mathsf{H}}_4^{+}$ and ${\mathsf{N}\mathsf{O}}_3^{-}$ leaching, especially in the intensive rainfall season. The combinations of HQ and DCD or Nitrapyrin significantly enhanced crop yield. Specifically, crop yields under A1 and A3 (1.5% HQ + 0.25% Nitrapyrin) were 16.3% and 14.3% higher than CK, respectively. The N stabilizing combinations also promoted N intake and transport at every growth stage. The maximum N accumulation was increased by 27% under A1, when compared to CK. The treatments supplied with urease/nitrification inhibitors also achieved higher apparent N recovery efficiency, N agronomic efficiency, and N partial factor productivity. Consequently, the combinations of urease/nitrification inhibitors could improve N availability at 0–40 cm soil layer, which in turn improved N use efficiency of wheat and maize. The results suggested that the two urease/nitrification inhibitor combinations, 1.5% HQ + 4% DCD (A1) and 1.5% HQ + 0.25% Nitrapyrin (A3), were optimal N stabilizing agents and worthy of further study.