Decomposition of litter mixtures generally cannot be predicted from the component species incubated in isolation. Therefore, such non-additive effects of litter mixing on soil C and N dynamics remain poorly understood in terrestrial ecosystems. In this study, litters of Mongolian pine and three dominant understory species and soil were collected from a Mongolian pine plantation in Northeast China. In order to examine the effects of mixed-species litter on soil microbial biomass N, soil net N mineralization and soil respiration, four single litter species and their mixtures consisting of all possible 2-, 3- and 4-species combinations were added to soils, respectively. In most instances, species mixing produced synergistic non-additive effects on soil microbial biomass N and soil respiration, but antagonistic non-additive effects on net N mineralization. Species composition rather than species richness explained the non-additive effects of species mixing on soil microbial biomass N and net N mineralization, due to the interspecific differences in litter chemical composition. Both litter species composition and richness explained non-additive soil respiration responses to mixed-species litter, while litter chemical diversity and chemical composition did not. Our study indicated that litter mixtures promoted soil microbial biomass N and soil respiration, and inhibited net N mineralization. Soil N related processes rather than soil respiration were partly explained by litter chemical composition and chemical diversity, highlighting the importance of functional diversity of litter on soil N cycling.