The use of protic ionic liquids (PILs) for the extraction of lignin from biomass has emerged as a promising and sustainable alternative to conventional methods.(1) However, the underlying mechanisms governing lignin dissolution, particularly the role of radical species in structural modifications and degradation, remain poorly understood. In this study, we employ electron paramagnetic resonance (EPR) spectroscopy to directly monitor and characterise radical formation during PIL-assisted lignin extraction.(2) By elucidating radical dynamics, we aim to optimise process conditions that enhance lignin recovery while preserving its native structure, ensuring industrial applicability. Our findings contribute to the development of more efficient and selective extraction strategies, ultimately advancing the valorization of lignocellulosic biomass in biorefinery applications.