The growth of zeolitic imidazolate framework (ZIF) thin films is an interesting topic, since ZIFs have a high thermal and chemical stability compared to many other MOFs. A variety of functionalities can be introduced via the imidazole linker molecule. Here, we report on a new approach for the preparation of thin films of a novel ZIF material: Co-ZIF-90. The preparation of thin films is possible on silicon or glass when ZIF-8 seeding layers are deposited first. The resulting constructions are effectively MOF-on-MOF layer systems. The synthesis procedure has been optimized with regard to obtaining high-quality thin films of Co-ZIF-90 on ZIF-8 for optical applications. Notably, the preparation of Co-ZIF-90 thin films is possible only by using a mixture of two different cobalt precursor salts (acetate and nitrate). The thin films are characterized in detail. With regard to the use as an optical material, UV-vis absorption spectra of the MOF-on-MOF constructs were measured and the refractive index of Co-ZIF-90 was determined using ellipsometry. Furthermore, the refractive index of the Co-ZIF-90 film can be modulated reversibly by the adsorption and desorption of water via the gas phase. The kinetics of this fast process are on the time scale of 1 s. In addition to the preparation of thin films, we obtained Co-ZIF-90 as a powder sample and basically characterized the powder. The approach to use an easy-to-crystallize ZIF-8 film as a seeding layer for the growth of films of other ZIFs may be extended as a general concept for the deposition of crystalline ZIF layers in such cases, where a direct deposition is difficult or not possible.