In extreme environments, it is difficult to balance the strength and toughness of ultra-thin film materials. To address this problem, we propose a promising strategy to build ultra strong, tough and extreme environments resistant Poly(p-phenylene-2,6-benzobisoxazole) (PBO) papers with a nacre-like structure constructed by synergistic electrostatic interaction and interlayer entanglement through the sol–gel-film method and hot press orientation. Highly interconnected PBO nanofibres (PNFs) with positive charges are tightly wound around the anisotropic graphene oxide (GO) nanosheets with negative charges through strong electrostatic interaction, forming a nacre like microstructure. The addition of Fe (Ⅲ) can form a coordination bond with the amino group on PNFs. Chemical crosslinking and hydrogen bonding synergize with interlayer entanglement effect among different PNFs,which can effectively dissipate interlayer energy and alleviate the conflict between strength and toughness. The resultant tensile strength and toughness are as high as 338.3 MPa and 16.04 MJ/m3,which are 197.7 % and 425.4 % of those of the intrinsic PBO paper, respectively. Additionally, after 5000 folding-unfolding cycles, the tensile strength retention and toughness retention of the PBO/GO/Fe (PGFe) paper were still 85.4 % and 71.9 %, respectively. Moreover, the paper exhibits excellent tolerance to extreme temperature environments and showed extremely strong chemical stability.