As automation systems become more common, there is growing interest in functional labeling systems using organic and inorganic hybrid materials. Especially, the demand for thermally and chemically stable labeling paper that can be used in a high temperature environment above 300 oC and a strong acid and base atmosphere is increasing. In this study, a composite coating solution for the development of labeling paper with excellent thermal and chemical stability is prepared by mixing a silica inorganic binder and titanium dioxide. The silica inorganic binder is synthesized using a sol-gel process and mixed with titanium dioxide to improve whiteness at high-temperature. Adhesion between the polyimide substrate and the coating layer is secured and the surface properties of the coating layer, including the thermal and chemical stability, are investigated in detail. The effects of the coating solution dispersion on the surface properties of the coating layer are also analyzed. Finally, it is confirmed that the developed functional labeling paper showed excellent printability.