The goal is to produce cottonized hemp fibers with improved thermal stability. It was first found that the fine hemp fibers produced from technical non-retted hemp fibers by steam explosion exhibited an enhanced thermal stability. An efficient and low-cost process was developed using a mixture of urea/etidronic acid in aqueous solution in order to achieve a high phosphorus content and produce flame retardant fibers by chemical grafting. ICP, 31P and 13C NMR, SEM, thermogravimetric, Pyrolysis-Combustion Flow Calorimetry analyses and a flame test were used to characterize the grafted fibers. Fibers modified with relatively high P and N contents have been produced (≈ 6 wt % and ≈ 4 wt % respectively) but lower grafting rates (P ≈ 0.5 % and N ≈ 0.35 %) are sufficient to produce non-flammable fibers. A synergistic effect between N and P has been proposed to induce the formation of a stable char.