The ecosystems of the Mediterranean interior dryland of Chile, dominated by an espinal agroecosystem of Acacia caven (Molina) Molina, show low productivity as a result of soil degradation. The objective of this study was to evaluate litter decomposition of A. caven and Lolium multiflorum Lam. in espinal ecosystems: well preserved (Wp) 50 to 80%, typical (Pd) 25 to 50%, and degraded (De) with 10 to 25% cover. During 420 d and starting in April 2004 until August 2005, weight loss in litter bags and chemical composition (hemicellulose, cellulose, lignin, nonstructural components, ash, N, C, C/N ratio, and P) were determined by using near infrared reflectance spectroscopy (NIRS) and the Van Soest protocol. Weight loss ranged from 31 to 52% in L. multiflorum and 26 to 40% in A. caven after 420 d. During the chemical decomposition process of L. multiflorum, cellulose degradation was relevant in the labile phase while lignin was important in the recalcitrant phase. On the other hand, non-structural components and cellulose were degraded in the labile phase and lignin in the recalcitrant stage for A. caven. Moreover, both litters improved N concentration during the decomposition process. Espinal ecosystems with higher canopy cover (Pd and Wp) had a positive influence, and showed early effects during the decomposition process, especially in the De espinal ecosystem, probably because of the microenvironmental conditions it generated. A better knowledge of the dynamics of litter decomposition in ecosystems was achieved by using both techniques: litter bags and NIRS.