Like most macromolecule polymers, epoxy resin (EP) is easy to burn, and there are great fire safety hazards in the process of use. Therefore, how to improve the fire safety of EP becomes one of the problems to be considered in the application of EP. In this study, tricobalt tetraoxide (Co3O4)-loaded TiO2 nanotube (TNT) (Co3O4-TNT) hybrid material was prepared by the co-precipitation method, and organophilic α-ZrP (OZrP) was obtained by hexadecyl trimethyl ammonium bromide-intercalated α-zirconium phosphate (α-ZrP) which was prepared by the hydrothermal synthesis method. Then, a series of nanocomposites were obtained by adding the synthesized nanomaterials to the EP at a certain ratio. The structure and morphology characterization indicated that Co3O4-TNTs and OZrP were synthesized successfully. The results of thermogravimetric analysis showed that the co-addition of Co3O4-TNTs and OZrP could further enhance the thermal stability of EP. The results of a cone calorimeter showed that EP/OZrP/Co3O4-TNTs had the lowest peak heat release rate and total heat release, which decreased by 36.2 and 35.4%, respectively, compared with the pure EP. This indicates that Co3O4-TNTs and OZrP had a good synergetic flame retardant effect and could effectively enhance the flame retardancy of EP.