Green, multifunctional protective fabrics have evoked enormous research enthusiasm because of the progress in public safety. Herein, inspired by the self-protection ability of natural creature, multifunctional protective cotton fabric (TP-Cotton) was prepared through layer-by-layer self-assembly of tannic acid (TA) and phytic acid (PA) from biomass. Due to the synergistic effect of TA as an antioxidant and PA as a fire retardant, the modified cotton fabric displays excellent fireproofing, antimicrobial activity, and UV-resistance. The limiting oxygen index of TP-Cotton reaches 39.4%, and the peak value of heat release rate (pHRR) reduces by 80.04% compared with Cotton. Moreover, the antibacterial rates of TP-Cotton against S. aureus and E. coli reaches 99.98 and 100.00%, respectively. Meanwhile, the ultraviolet protection factor value is over 40 due to the integration of TA, which is rich in phenolic hydroxyl groups. Therefore, benefiting from this unique composition and the simple preparation strategy, the as-prepared cotton fabrics showed highly multiple protection capabilities, having promising applications as protective clothing, military uniform, and overalls for emergency services.