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Poly(vinylphosphonic acid) (PVPA) and polyethylenepolyamine (PEPA) are used as novel intumescent flame retardants to improve the properties of MXene (2D Ti₃C₂T<i>_x</i>)/poly(vinyl alcohol) (PVA) nanocomposites. We investigated the flame-retardant properties, thermal stability, and mechanical properties of MXene/PVA nanocomposites. The results show that MXene was homogeneously dispersed in the PVA matrix containing PVPA and PEPA. PVPA and PEPA effectively improved the flame-retardant properties of MXene/PVA nanocomposites and they did not obviously change the thermal degradation of the MXene/PVA nanocomposites. Moreover, MXene improved the thermal stability of the PVA matrix. The elongation at break of MXene/PVA nanocomposites reached its maximum when the MXene mass fraction was 1.0 wt.%, regardless of whether PVPA and PEPA were present in the PVA matrix, whereas the tensile strength and Young’s modulus of MXene/PVA nanocomposites increased with the increase in MXene content in the PVA matrix.