Titania-supported vanadia (VO_x/TiO₂) catalysts exhibit outstanding catalytic in a number of selective oxidation and reduction processes. In spite of numerous investigations, the nature of redox transformations of vanadium and titanium involved in various catalytic processes remains difficult to detect and correlate to the rate of products formation. In this work, we studied the redox dynamics of active sites in a bilayered 5% V₂O₅/15% TiO₂/SiO₂ catalyst (consisting of submonolayer VO_x species anchored onto a TiO_x monolayer, which in turn is supported on SiO₂) during the oxidative dehydrogenation of ethanol. The VO_x species in 5% V₂O₅/15% TiO₂/SiO₂ show high selectivity to acetaldehyde and an ca. 40 times higher acetaldehyde formation rate in comparison to VO_x species supported on SiO₂ with a similar density. Operando time-resolved V and Ti K-edge X-ray absorption near-edge spectroscopy, coupled with a transient experimental strategy, quantitatively showed that the formation of acetaldehyde over 5% V₂O₅/15% TiO₂/SiO₂ is kinetically coupled to the formation of a V⁴⁺ intermediate, while the formation of V³⁺ is delayed and 10–70 times slower. The low-coordinated nature of various redox states of VO_x species (V⁵⁺, V⁴⁺, and V³⁺) in the 5% V₂O₅/15% TiO₂/SiO₂ catalyst is confirmed using the extensive database of V K-edge XANES spectra of standards and specially synthesized molecular crystals. Much weaker redox activity of the Ti⁴⁺/Ti³⁺ couple was also detected; however, it was found to not be kinetically coupled to the rate-determining step of ethanol oxidation. Thus, the promoter effect of TiO_x is rather complex. TiO_x species might be involved in a fast electron transport between VO_x species and might affect the electronic structure of VO_x, thereby promoting their reducibility. This study demonstrates the high potential of element-specific operando X-ray absorption spectroscopy for uncovering complex catalytic mechanisms involving the redox kinetics of various metal oxides.