Boron nitride nanosheet (BNNS) decorated with cobalt ferrite nanoparticle (CFN) to afford CFN-BNNS nanohybrid was prepared via a simple hydrothermal route and was well characterized. Subsequently, the as-prepared CFN-BNNS nanohybrid was incorporated into epoxy resin (EP) with the introduction of a weak rotary magnetic field to achieve order orientation, in order to reduce the fire risk and toxic hazards using enhanced shielding effect of BNNS upon combustion. Findings demonstrate that the CFN-BNNS nanohybrid is composed of CFN nanoparticle uniformly dispersed on BNNS surface. Thermal analysis and cone calorimeter data show that the CFN-BNNS nanofiller among EP matrix contributes to improving the char residues and mechanical properties of EP and reducing its fire risk as well as toxic hazards, especially the ordered one is advantageous over the disordered one in reducing the fire risk and toxic hazard. This is because, on the one hand, the orderly aligned BNNS as the physical barrier can more effectively prevent the transfer and diffusion of oxygen and heat. On the other hand, CFN can catalyze the degradation of EP to afford excessive chars on polymer surface; and it is also liable to decomposition during combustion, thereby generating ferrite species to promote EP degradation as well as cobalt species to enhance the oxidation of CO.