Poly(p-phenylene-2,6-benzobisoxazole) nanofiber (PNF) paper is facing unprecedented challenges in enhancing the interaction between the PNFs and improving its hydrophobicity. In this work, a sol–gel film transformation approach was developed to fabricate high-strength PNF paper. Iron ions formed coordination bonds between PNFs to obtain a preforming three-dimensional, interconnective nanofiber network. Subsequently, polytetrafluoroethylene (PTFE) particles were sprayed onto the surface of the paper, followed by thermal treatment to obtain double-layered PTFE-P/PNF nanocomposite paper. The nanocomposite paper presents incredible tensile strength (271.6 MPa, increased by 52.9%), folding endurance, super-hydrophobicity, and self-cleaning performances. Moreover, it exhibits low dielectric constant (2.06) and dielectric loss tangent (0.0133) values. According to the wave-transparent model for a double-layered dielectric established by Maxwell’s equations, the wave-transparent coefficients of electromagnetic waves incident from both sides of the paper are 97.6% (PNF side) and 96.0% (PTFE/P(S-co-BCB-co-MMA) side), respectively. The PTFE-P/PNF nanocomposite paper possesses great potential in the fields of wave-transparent applications.