(1) Background: In managing ecological tea gardens, litter composed of pruned and fallen tea leaves from companion tree species is an important component of tea garden soil. The decomposition of litter plays a crucial role in regulating nutrient cycling in tea garden ecosystems. (2) Methods: This study employed the litterbag method to investigate chemical stoichiometry characteristics and enzyme activity changes during the decomposition process of pruned and fallen Camellia sinensis leaves from companion tree species in an ecological tea garden located in central Guizhou Province. (3) Results: With decomposition duration, the general trend of changes in the C/N and C/P ratios showed a decrease in the activity of UE (urease), AP (acid phosphatase), and PPO (polyphenol oxidase) followed by an increase, while CAT (catalase) and CEL (cellulase) activity decreased, then increased, and then decreased again. On the other hand, the N/P and the activity of SC (sucrase) first increased and then decreased. The C/N and the activities of UE, PPO, and AP generally reached their maximum values during the late decomposition stage (366-428 d), while the N/P and the CAT activity peaked during the mid-decomposition stage (305 d). In contrast, the activity of SC and CEL reached its maximum value during the early decomposition stage (123 d). The N/P ratios were significantly higher than those of the CS (C. sinensis) litter in the mixed treatment, while C/N and C/P ratios were significantly lower than those in the CS during decomposition for 184-366 days. The UE, CAT, AP, and SC activities of CBL (C. sinensis + B. luminifera) litter were significantly higher than those of the CS litter during decomposition. During the experiment, antagonistic effects were observed in the C/N and C/P ratios of the different litter types. Most mixed litter exhibited additive effects on enzyme activity, while a few showed nonadditive effects. For the nonadditive effects, most were antagonistic effects, mainly in the CPM (C. sinensis + C. glanduliferum) litter. A small portion, mainly observed in the CBL and CCG (C. sinensis + C. glanduliferum) litter, showed synergistic effects. (4) Conclusions: Selecting B. luminifera and C. glanduliferum to be part of the tree species composition in ecological tea gardens can produce positive mixed effects on enzyme activity during litter decomposition, increase nutrient return capacity, maintain tea garden fertility, and achieve the ecological development of tea gardens.
