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The SiO 2 @metal organic framework (Universitetet i Oslo-66, UiO-66) core–shell microspheres were constructed through covalent linkage between amine groups in UiO-66-NH 2 and epoxy groups on the surface of silica. The morphology and size of the SiO 2 @UiO-66 core–shell microspheres could be simply controlled by tuning the ratio between UiO-66-NH 2 and epoxy terminated silica (E-SiO 2). As observed by TEM, the SiO 2 @UiO-66 hybrids showed better dispersion state within epoxy matrix compared to either E-SiO 2 or UiO-66-NH 2. The incorporation of SiO 2 @UiO-66 hybrids slightly promoted the thermal degradation of the resultant epoxy composites but improved residual yield. The dynamic mechanical analysis results indicated that the SiO 2 @UiO-66 hybrids slightly increased the glass transition temperature and the modulus. The SiO 2 @UiO-66 hybrids exhibited higher efficiency in reducing the heat release rate and the smoke production rate compared to either E-SiO 2 or UiO-66-NH 2. The influence of the component ratio in SiO 2 @UiO-66 on flame retardancy of the epoxy composites was also studied by cone calorimeter. Specifically, the SiO 2 @UiO-66 hybrid with medium ratio (SiO 2 @UiO-66-2) exhibited maximum reduction in peak heat release rate (−31%), total heat release (−23%) and total smoke production (−16%). The char residues were investigated by the Fourier transform infrared spectra, scanning electron microscopy and X-ray photoelectron spectroscopy, which demonstrated that the enhanced flame retardancy of EP/SiO 2 @UiO-66-2 was attributable to the continual morphology and high thermal resistance originated from the presence of the silicon and zirconium complex. These favorable characteristics including high flame retardant efficiency and good smoke suppression make SiO 2 @UiO-66 hybrids promising for flame retardant polymers application. • The SiO 2 @UiO-66 hybrids showed core–shell microsphere structure. • The addition of 3 wt% SiO 2 @UiO-66-2 caused 31% reduction in peak heat release rate. • The addition of 3 wt% SiO 2 @UiO-66-2 led to 16% reduction in total smoke production. [ABSTRACT FROM AUTHOR]