Exploring the native defects of zeolites is highly important for understanding the properties of zeolites, such as catalysis and optics. Here, ITQ-16 films were prepared via the secondary growth method in the presence of Ge atoms. Various intrinsic defects of ITQ-16 films were fully studied through photoluminescence and FTIR characterizations. It was found that both the as-synthesized and calcined ITQ-16 films displayed multicolor photoluminescence including ultraviolet, blue, green and red emissions by exciting upon appropriate wavelengths. The results indicate that Si―OH and non-bridging oxygen hole centers(NBOHCs) are responsible for the origin of green and red emissions at 540―800 nm, while according to a variety of emission bands of calcined ITQ-16 film, blue emission bands at around 446 and 462 nm are attributed to peroxy free radicals(≡SiO2), ultraviolet emissions ranging from 250 nm to 450 nm are suggested originating from a singlet-to-triplet transition of two-fold-coordinated Si and Ge, respectively. © 2016, Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH.