This article investigates the effects of combining a novel protic ionic liquid-based fire retardant (FR) with alkalized hemp fiber. A pivotal importance of this study refers to the hydrophilic properties and limits regarding poor thermal resistance of green composites where standard guidelines for fire risks are crucial. Although it is well-studied that alkalization is essential for green composite’s moisture and mechanical durability, research on the flammability of such a combined treatment for natural fiber-reinforced biopolymer composites is lacking. The alkaline treatment used in the current study follows a process already studied as optimal, particularly for the selected hemp fiber. The fire performance was examined using a bench scale approach based on self and piloted ignition from cone calorimeter tests. The result from the Fourier-transform infrared analysis of the hemp fiber confirms phosphorylation following the fire-retardant treatment, which was visible from the morphological examination with scanning electron microscope. The presence of FR in the composites led to impactful moisture sorption. However, the FR composites demonstrated an enhanced response to fire, indicating potential use as a Class B standard for building construction, and hazard level 3 (HL3) classification as an interior material in vehicles, provided the problem of high emission of smoke is mitigated.