Peatlands, storing significant amounts of carbon, are extremely vulnerable to climate change. The effects of climate change are projected to lead to a vegetation shift from Sphagnum mosses to sedges and shrubs. Impacts on the present moss-dominated peat remain largely unknown. In this study, we used a multiproxy approach to investigate the influence of contrasting vascular plant types (sedges, shrubs) on peat chemistry and decomposition. Peat cores of 20 cm depth and plant material (Sphagnum spp., Calluna vulgaris and Eriophorum vaginatum) from two ombrotrophic peatlands in the Italian Alps with a mean annual temperature difference of 1.4 °C were analyzed. Peat cores were taken under adjacent shrub and sedge plants growing at the same height above the water table. We used carbon, nitrogen and their stable isotopes to assess general patterns in the degree of decomposition across sampling locations and depths. In addition, analytical pyrolysis was applied to disentangle effects of vascular plants (sedge, shrub) on chemical properties and decomposition of the moss-dominated peat. Pyrolysis data confirmed that Sphagnum moss dominated the present peat irrespective of depth. Nevertheless, vascular plants contributed to peat properties as revealed by, e.g., pyrolysis products of lignin. The degree of peat decomposition increased with depth as shown by, e.g., decreasing amounts of the pyrolysis product of sphagnum acid and increasing °13C with depth. Multiple parameters also revealed a higher degree of decomposition of Sphagnum-dominated peat collected under sedges than under shrubs, particularly at the high temperature site. Surprisingly, temperature effects on peat decomposition were less pronounced than those of sedges. Our results imply that vascular plants affect the decomposition of the existing peat formed by Sphagnum, particularly at elevated temperature. These results suggest that changes in plant functional types may have a stronger impact on the soil carbon feedback in a warmer world than hitherto assumed.