The decomposition of litter carbon (C) fraction is a major determinant of soil organic matter pool and nutrient cycling. However, knowledge of litter chemical traits regulate C fractions release is still relatively limited. A litterbag experiment was conducted using six plant functional litter types at two vegetation type (coniferous forest and alpine shrubland) in a treeline ecotone. We evaluated the relative importance of litter chemistry (i.e. Nutrient, C quality, and stoichiometry) on the loss of litter mass, non-polar extractables (NPE), water-soluble extractables (WSE), acid-hydrolyzable carbohydrates (ACID), and acid-unhydrolyzable residue (AUR) during decomposition. Litter nutrients contain nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), sodium (Na), magnesium (Mg), aluminium (Al), manganese (Mn), zinc (Zn), iron (Fe) and copper (Cu), litter C quality contains C, WSE, NPE, ACID, and AUR, and stoichiometry was defined by C:N, C:P; N:P, ACID:N, and AUR:N. The results showed single exponential model fitted decomposition rates of litter mass and C fractions better than double exponential or asymptotic decomposition, and the decomposition rates of C fractions were strongly correlated with initial litter nutrients, especially K, Na, Ca. Furthermore, the temporal dynamics of litter nutrients (Ca, Mg, Na, K, Zn, and Fe) strongly regulated C fractions loss during the decomposition process. Changes in litter C quality had an evident effect on the degradation of ACID and AUR, supporting the concept of “priming effect” of soluble carbon fraction. The significant differences were found in the release of NPE, WSE, and ACID rather than AUR among coniferous forest and alpine shrubland, and the vegetation type effects largely depend on the changes in litter stoichiometry, which is an important implication for the change in plant community abundance regulate decay. Collectively, elucidating the hierarchical drivers of litter chemistry on decomposition is critical to soil C sequestration in alpine ecosystems.