The reconstruction of past climates and vegetation can provide valuable information for understanding the mechanisms of the variability of the East Asian summer monsoon in eastern China. In this study, organic geochemical evidence from the compositions of sedimentary leaf-wax stable isotopes and n-alkane parameters investigates the changes in vegetation and climate over the last 1200 years in the Xiyaohu peatland, Jiangxi Province, southeast China. Combined with temperature records, three climatic periods are presented: (a) a warm and humid period with an increase in C4 plants from 900 to 1450 AD, which coincides with the Medieval Warm Period (MWP); (b) a cool and dry period with the expansion of C3 plants from 1450 to 1800 AD, coinciding with the Little Ice Age (LIA); and (c) the Present Warm Period (PWP) from 1800 AD until the present, with warm and wet conditions. The sub-stages within the MWP and LIA intervals are also presented. The earlier MWP stage (900–1125 AD) was drier than the latter one (1125–1450 AD), and the earlier LIA stage (1450–1650 AD) was drier than the late LIA (1650–1800 AD). Increased solar irradiance and enhanced El Niño activities are related to the warm and humid climate during the MWP and PWP, whereas reduced solar irradiance and La Niña activities correspond to the cool and dry climate during the LIA. The present results provide insights into paleoclimatic changes in eastern monsoonal China and provide an understanding of centennial-scale climatic fluctuations and their driving factors.