The present paper continues the exploration of the physicochemical and catalytic properties of vanadia-mayenite composites. The samples were prepared by an impregnation of calcium aluminate Ca12Al14O33 (mayenite, C12A7) with a solution of vanadium precursor. Pure mayenite and V/C12A7 nanocomposites were characterized by Raman and diffuse reflectance UV–Vis spectroscopies. The reducibility of the samples was examined in temperature-programmed reduction experiments performed in a hydrogen atmosphere. The catalytic performance of vanadium-containing systems was studied in the non-oxidative dehydrogenation of ethane. As found, the low-loaded sample (5%V/C12A7 sample) contains vanadium predominantly in the form of Ca3(VO4)2, while for the 10%V/C12A7 sample, two types of calcium vanadates (Ca2V2O7 and Ca3(VO4)2) are registered. The presence of these phases defines the spectroscopic characteristics and the redox properties of nanocomposites. Both the samples, 5%V/C12A7 and 10%V/C12A7, exhibit comparable catalytic activity, which is mainly connected with the amount of the Ca3(VO4)2 phase. The uniqueness of the studied catalysts is their excellent tolerance toward coke formation under the reaction conditions.