Abstract Smart multifunctional textiles are strongly demanded for their advantages of ensuring comfort, safety, and durability for human security protection, but they remain greatly challenged in the structure design and performance improvement. Herein, a novel Coolmax/cotton woven fabric with dual‐faced structures (DFS) is fabricated, then spray coated with polydimethylsiloxane composite, and its comprehensive characterizations are fully evaluated. Janus configuration facilitates rapid directional water transport from the hydrophobic inner layer to the hydrophilic outer layer within 4.6 ± 0.45 s, thereby substantially enhancing thermal‐moisture comfort under conditions of intense physical exertion and elevated temperatures. Flame retardancy is also imparted through a facile single‐layer dip‐coating strategy employing chitosan (CS)/phytic acid (PA)/ TiO 2 . Notably, introducing only 0.5 wt.% TiO 2 led to a significant increase in char residue, reaching at 7.61%. Sample CS‐PA@TiO 2 (titanium dioxide) showed self‐extinguishing behavior in the vertical burning test, as well as a significantly enhanced limiting oxygen index (LOI) to 35.3 ± 1.93 from 19.03 ± 1.25 for pure DFS fabric, and those of peak heat release rate and total heat release for sample CS‐PA@TiO 2 is drastically declined by 65% and 47%, respectively. Moreover, the fabric maintained adequate mechanical strength and abrasion resistance, indicating excellent durability under repeated wear. This work will provide synergistically integrated multifunctional textiles through a simple, scalable approach.