In boreal peatlands, litter decomposition plays an important role in modulating ecosystem carbon (C) cycling and nutrient turnover. However, how climate warming and plant functional group interact to affect litter decomposition is still unclear in these ecosystems. Here, we collected fresh litters of six plant functional groups (nitrogen (N)-fixing species, deciduous tree, deciduous shrub, evergreen shrub, graminoid, and Sphagnum moss) from a boreal peatland located in northeast China. A laboratory incubation experiment was used to determine the effect of temperature (10 °C vs. 20 °C) on microbial respiration and mass loss during decomposition. Among the six functional groups, the litters of N-fixing species and deciduous shrub, followed by deciduous tree, generally had the greatest mass losses and microbial respiration rates, whereas the Sphagnum moss decomposed with the slowest rate at both incubation temperatures. Increasing incubation temperature from 10 °C to 20 °C, microbial respiration rate and mass loss increased slightly for Sphagnum moss litters (25% and 19%, respectively), but increased dramatically for vascular plant litters (84–135% and 49–85%, respectively). For litters from vascular plants, both decomposition rate and temperature sensitivity showed a tight linear correlation with the initial C:N and C:phosphorus ratios. Considering that climate warming will cause increased dominance of woody plant species coupled with decreased cover by Sphagnum mosses, this study provides clear evidence that climate warming and the associated changes to vegetation community composition can synergistically accelerate plant litter decomposition in boreal peatlands.