With the continuing increase in human activities, ecologists are increasingly interested in understanding the effects of acid rain on litter decomposition. Two dominant litters were chosen from Zijin Mountain in China: Quercus acutissima from a broad-leaved forest and Pinus massoniana from a coniferous forest. The litters were incubated in microcosms and treated with simulated acid rain (gradient pH levels). During a six-month incubation, changes in chemical composition (i.e., lignin, total carbohydrate, and nitrogen), litter mass losses, soil pH values, and activities of degradative enzymes were determined. Results showed that litter mass losses were depressed after exposure to acid rain and the effects of acid rain on the litter decomposition rates of needles were higher than on those of leaves. Results also revealed that simulated acid rain restrained the activities of cellulase, invertase, nitrate reductase, acid phosphatase, alkaline phosphatase, polyphenol oxidase, and urease, while it enhanced the activities of catalase in most cases during the six-month decomposition process. Catalase and polyphenol oxidase were primarily responsible for litter decomposition in the broad-leaved forest, while invertase, nitrate reductase, and urease were primarily responsible for litter decomposition in the coniferous forest. The results suggest acid rain-restrained litter decomposition may be due to the depressed enzymatic activities. According to the results of this study, soil carbon in subtropical forests would accumulate as a long-term consequence of continued acid rain. This may presumably alter the balance of ecosystem carbon flux, nutrient cycling, and humus formation, which may, in turn, have multiple effects on forest ecosystems.