A lustrous appearance and interference-based colors make pearlescent pigments attractive for use in applications such as automotive paints, plastics, consumer electronics, and cosmetics. A combination of interference and absorption in the visible light spectrum improves significantly the hiding power as well as the color strength of pearlescent pigments while potentially extending their color range. The aim of the present study was to introduce synthetic fluorohectorites, having an appreciable diameter (~20 μm) and aspect ratio (~1000), as promising colored cores for pearlescent pigments. Fluorohectorites can adopt a variety of colors by ion-exchange reaction with cationic organic dyes of high absorption coefficient. Unlike related dye-exchanged natural montmorillonite clays, which undergo acid activation accompanied by release of dye at low pH, as is required for subsequent coating with TiO2 in an environment with low pH and elevated temperature, no leaching was observed with dye-exchanged synthetic fluorohectorites ([Na0.5]int.[Mg2.5Li0.5]oct.[Si4]tet.O10F2). Due to its significantly greater layer charge, more organic dye molecules were adsorbed per volume of the fluorohectorite than for montmorillonite. Consequently, the free volume available in the interlayer space for H3O+ diffusion was less for synthetic fluorohectorite than for montmorillonite. Acid attack via interlayer space was, therefore, retarded significantly for fluorohectorite. Acid attack from the external edges of synthetic fluorohectorites was in the range of conventionally applied mica pigment core (fluorophlogopite, ([K]int.[Mg3]oct.[AlSi3]tet.O10(F,OH)2) because of the comparable large diameter of the platelets. Montmorillonite, however, occurs with particle diameters typically <200 nm and the much increased relative contribution of edges to the total surface area also makes them more prone to acid attack and concomitant leaching. Aside from leaching stability, the confinement of organic dyes in the interlayer space restricts rotational and vibrational motions, which in turn stabilizes the dyes typically by ~100°C against thermal decomposition as compared to chloride salts of the dyes.