Dissolved organic matter is a key compartment for biogeochemical cycles in the Arctic and Subarctic terrestrial environments. With changing vegetation ecosystems, the chemical composition of organic matter is expected to shift and thus, the most labile part of it, namely the extractable fraction. To this date, few studies have focused on the fingerprinting of DOM fraction from different primary sources, and even less on its potential repercussions on the environment. In this study, we jointly characterized the chemical composition of bulk and water-extractable organic matter (WEOM) from different vegetation species typical of Subarctic ecosystems. Through a multi-analyses approach, including elementary analysis, solid state 13C nuclear magnetic resonance, UV and 3D fluorescence spectroscopy, and high-resolution mass spectrometry, our results highlighted that the quantity and composition of produced WEOM significantly differed between vegetation sources and specifically between plant functional types (PFT, e.g., lichens, graminoids, and trees and shrubs). The relevance of optical indices was questioned, and the use of several of them was discarded for unprocessed WEOM study. However, the DOM proxies (optical indices, molecular composition, and stoichiometry) enabled to conclude that the lichen WEOM was likely less degradable than vascular plants WEOM, and among the latter group, graminoids produced more degradable WEOM than trees and shrubs. This work reported specific organic fingerprints for the different PFT. Consequently, the ongoing changes of vegetation in Arctic and Subarctic regions may greatly affect the composition of DOM that enters the soil and the hydrosystems, as well as the biogeochemical processes it is involved in.