We formulate for the first time new [Alizarin-poly(4-vinylpyridine)-mica] inorganic@organic pH dependent pigmentary materials. The present formulation is carried out via two steps: (i) the preparation by adsorption of poly(4-vinylpyridine) [P4VP] on mica particles, of two hybrid composite materials [P4VP@Mica], with respectively ratios R ¼ 0.2 and R ¼ 0.5; (ii) the formulation of new pigmentary materials by fixation of Alizarin dyes on [P4VP@Mica] composite materials. The composite materials [P4VP@Mica] were characterized using, Thermogravimetric analysis (TGA), Fourier transformed infrared (IRTF), Scanning Electron Microscopy coupled with Energy dispersive X-Ray Spectroscopy (SEM-EDX) and UV-visible. The adsorbed polymers on the inorganic surface have a potential interest for the modification of the interfacial properties of the MICA. These new pigmentary materials can either differ by their colors, or to present interferential effects.