Leaf and root litter decomposition has been a major research focus. However, the possible effects of belowground microbial community structure and diversity on this process are poorly understood. Understanding the biochemical mechanisms controlling aboveground decomposition processes is important to predict the changes of soil carbon and nutrient cycling in response to changes of forest management regimes. Here, we explore the biochemical controls of leaf and fine root decomposition in three subtropical plantations (Ford Erythrophleum (Erythrophleum fordii Oliver), Masson Pine (Pinus massoniana Lamb.)), and a mixed plantation containing both species) using the litterbag method, and soil microbial communities were determined using phospholipid fatty acid profiles. Overall, leaves decomposed more rapidly than fine roots, potentially due to the faster degradation of their cellulose component, but not lignin. In addition, leaf and fine root decomposition rates varied among plantations, being higher in E. fordii and lower in P. massoniana. Substrate quality such as N, Ca, lignin concentration, and C/N ratio were responsible for the decomposition rate changes among plantation types. Moreover, we used redundancy analysis to examine the relationships between litter decomposition and soil microbial community composition and diversity. Results revealed that actinobacteria and arbuscular mycorrhizal fungi community were the key determinants affecting leaf and fine root litter decomposition, respectively. Our work demonstrates that litter decomposition was linked to substrate quality and to the structure of soil microbial communities, and evidences the probable role of E. fordii in increasing soil nutrient availability, especially N, P and Ca. Additional data on phospholipid fatty acid (PLFA) or DNA marker groups within the litterbags over time may provide insights into litter decomposition dynamics, which represents potential objectives for future long-term decomposition studies.