Interest in wearable electronics has led to extensive studies on woven textiles that are mechanically robust and stretchable, have high electrical conductivities, and exhibit fire resistance properties even at high temperatures. We demonstrate a highly easy and scalable method for fabricating defect-free graphene (df G) nacrebased woven electronic textiles (e-textiles) with enhanced flame-retardant properties and high electronic conductivities. The as-prepared graphene shows perfect preservation of its inherent properties without any crystal damage during subsequent exfoliation and noncovalent melamine functionalization. The defect-free graphene functionalized by melamine (m-df G) is well dispersed in various polar solvents. To investigate the synergistic effect of m-df G, quaternary artificial nacre composites are fabricated by adding manganese(II) chloride to a m-df G/ polymer (carboxymethyl cellulose (CMC)) composite. Their mechanical, electrical, and thermal characteristics are then evaluated. The quaternary m-df G-Mn2+-CMC artificial nacre exhibits exceptionally enhanced mechanical properties (tensile strength: 613.9 MPa; toughness: 7.13 MJ m−3 ) and the best flame retardancy (even at torch heating) as compared to those of graphene oxide/reduced graphene oxide (GO/rGO)-based nacres. In this context, our approach will be helpful to future wearable electronics and fire-retardant textiles with high strength, which can accelerate the commercial viability of e-textiles.