Root detritusphere is one of the most important sources of N2O, however, understanding of how N2O emission from the detritusphere is influenced by soil properties remains elusive. Here, we evaluated the effects of pore architecture and soil moisture on N2O emission during the decomposition of in-situ grown roots of switchgrass, an important bioenergy crop. We combined dual isotope labeling (15C and 15N) with zymography to gain insights into the location of the microbial N2O production in soils with contrasting pore architectures. In the studied soil, the effect of soil pore architecture on N2O emissions was 6 times greater than that of soil moisture. Soil dominated by > 30 μm Ø pores (i.e., large-pore soil) had higher chitinase activity than the soil dominated by < 10 μm Ø pores (i.e., small-pore soil), especially near the decomposing roots. The chitinase activity on the decomposing roots was positively correlated with emission of root-derived N2O, indicating that N released from root decomposition was an important source of N2O. Greater N2O and N2 emission was induced by switchgrass roots in soils dominated by the large- compared to the small-pore soils. The microenvironment developed near decomposing roots of the large-pore soil also resulted in positive N2O priming. Our study challenged the traditional view on soil moisture as the main factor of N2O production. Production and emission of N2O was most intensive in microbial activity hotspots (i.e., rhizosphere legacy) in the large pores, where decomposed roots release mineral N as the main N2O source. © 2022