In this work, sandwich-like structured CoAl-LDH@ZIF-67 hybrids were constructed by in situ growth of nanosized ZIF-67 crystallites on CoAl-LDH nanoplates. The structure and morphology of CoAl-LDH@ZIF-67 hybrids were represented by X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Transmission Electron Microscopy (TEM). Accordingly, the hybrids were introduced into epoxy resins to explore their effect on the thermal and fire safety properties of epoxy composites. With the introduction of 2% CoAl-LDH@ZIF-67 hybrids, the T_10%, T_50% and T_max values were decreased to some extent and the char residue yield was higher than that of pristine epoxy. The peak heat release rate (PHRR) of epoxy composites declined by 26.4%, in comparison with those of pure epoxy. Moreover, the quantity of smoke produced, toxic CO released and CO₂ produced were suppressed markedly and decreased by 16.7%, 59.8% and 32.2%, respectively. A possible mechanism for improving fire safety was put forward based on the analysis of the carbon residues.