Litter decomposition is a key regulator of soil carbon formation and nutrient cycling in the plant–soil continuum. However, the utility of structural chemical indicators for capturing the relationship between litter decomposition and environmental factors under nitrogen (N) enrichment remains unclear. We conducted a two-year in situ decomposition experiment with different N addition treatments in a pure Quercus variabilis forest on the Qinling Mountains, China. During the active six-month growing season, we investigated the stoichiometric ratios of typical organic acids in litter and soil layers and their responses to soil environments. The total relative content of the four organic acids showed the most pronounced nonlinear shift along the N addition gradient, peaking at N75 (7.5 g N m⁻²) then declining. The stoichiometric ratios of some typical organic acids varied analogously to soil physicochemical properties, microbial diversity and abundance. This inter-annual response was particularly pronounced in the warmer and wetter year of 2023. Structural chemical analysis revealed that steric hindrance and molecular symmetry are key factors regulating the decomposition efficiency of typical organic acids in litter. Notably, phenolic acid and butyric acid isomer ratios exhibited significant subgroup-specific responses to soil physicochemical factors, enzyme activities, and microbial abundances. Collectively, these ratios may indicate N addition impacts on litter decomposition, hold potential for predicting climatic variability responses, and provide conceptual support for an integrated framework linking N enrichment, litter chemistry, and soil carbon dynamics in temperate forests.