Inorganic pigments are a commonly used colorant with various applications and promising prospects. However, the implement of organic pigments is hindered by poor dispersion stability in coatings due to non-uniform morphology and size. Herein, encapsulated pigments of Cobalt Chrome Green CoCr2O4 (PG 26), Cobalt Blue CoAl2O4 (PB 28), Titanium Chrome Yellow TiCrSbO6 (PB 24) in epoxy microspheres are obtained via an oil-in-water emulsion polymerization. The morphology, particle size, thermal properties, glass transition temperature (Tg) and color performance of the composite microspheres were characterized by different analytical techniques. The average particle size varied with pigments types and loadings. When the content of CoCr2O4 and CoAl2O4 is in the range of 15 wt%-30 wt%, and TiCrSbO6 content is between 15 wt%-25 wt%, the composite microspheres exhibit a narrow particle size distribution, regular morphology, and smooth surface. The size followed the rule of CoAl2O4/epoxy (20–26 μm) > CoCr2O4/epoxy (14-16μm) > TiCrSbO6/epoxy (6–9 μm). Besides, according to the aggregation-induced emission (AIE) principle, the relationship between fluorescence intensity and reaction time was investigated, thus deducing the curing process of the epoxy groups with m-xylenol dimethylamine (MXDA). The kinds of three inorganic fillers exhibit varying effects on the diffusion process of MXDA. TiCrSbO6 promotes the progress of the epoxy-amine curing reaction. Notably, CoCr2O4 microspheres exhibited stable green value (a*) and color saturation (C*), TiCrSbO6 microspheres showed increased yellow value (b*) and saturation (C*), and CoAl2O4 microspheres enhanced blue value (b*) with minimal change in lightness (L*). Overall, this study provides a comprehensive understanding of the properties of inorganic pigment/epoxy composite microspheres and highlights their potential for improved dispersion stability in coating applications.