Peat carbon accumulation is controlled by both large scale factors, such as climate and hydrological setting, and small scale factors, such as microtopography and plant community. These small scale factors commonly vary within peatlands and can cause variation in biogeochemical traits and carbon accumulation within the same site. To understand these within-site variations, we investigated long term carbon accumulation, peat decomposition, biogeochemistry of pore water and plant macrofossils along a transect in an ombrotrophic bog in southern Patagonia. An additional question we addressed is how historical deposition of volcanic ash on the peatland has affected its carbon balance. Variability in plant community and water table led to differences in long term peat and carbon accumulation (peat moss > cushion plant), organic matter decomposition (cushion plant > peat moss), and methane production (peat moss > cushion plant). Macrofossil analysis and radiocarbon dating indicated a relationship between plant community and carbon accumulation or decomposition during the historical succession of vegetation in the peatland. C/N ratio and isotopic signatures reflected variability in plant community as litter source, and DOC concentrations were controlled by humification level. Volcanic ash deposition had only limited effect on plant composition, but it was associated with increased decomposition in overlying peat layers. This study highlights the importance of understanding how plant communities develop, as changes in communities could significantly affect the potential of ombrotrophic peatlands as C sink.