China is among the top nitrous oxide (N2O)-emitting countries, but existing national inventories do not provide full-scale emissions including both natural and anthropogenic sources. We conducted a four-decade (1980–2020) of comprehensive quantification of Chinese N2O inventory using empirical emission factor method for anthropogenic sources and two up-to-date process-based models for natural sources. Total N2O emissions peaked at 2287.4 (1774.8–2799.9) Gg N2O yr−1 in 2018, and agriculture-developed regions, like the East, Northeast, and Central, were the top N2O-emitting regions. Agricultural N2O emissions have started to decrease after 2016 due to the decline of nitrogen fertilization applications, while, industrial and energetic sources have been dramatically increasing after 2005. N2O emissions from agriculture, industry, energy, and waste represented 49.3%, 26.4%, 17.5%, and 6.7% of the anthropogenic emissions in 2020, respectively, which revealed that it is imperative to prioritize N2O emission mitigation in agriculture, industry, and energy. Natural N2O sources, dominated by forests, have been steadily growing from 317.3 (290.3–344.1) Gg N2O yr−1 in 1980 to 376.2 (335.5–407.2) Gg N2O yr−1 in 2020. Our study produces a Full-scale Annual N2O dataset in China (FAN2020), providing emergent counting to refine the current national N2O inventories.