Vinylidene fluoride (VDF) is a fundamental fluorinated olefin in the fluorochemical industry, and innovation in its production holds significant importance for sustainable development. Traditional routes involving the dehydrohalogenation or dehalogenation of halogenated alkanes suffer from issues such as substantial waste emissions and severe equipment corrosion. The one-step catalytic dehydrogenation of 1,1-difluoroethane (HFC-152a) to produce VDF offers notable advantages. To accomplish this goal, this work innovatively aims to construct an oxidative dehydrogenation system with a highly dispersed Mo/Ti catalyst for HFC-152a. Through systematic characterization techniques, such as XPS, XRD, Raman spectroscopy, and TPD, the reaction mechanism is thoroughly investigated. These results prove that more abundant O2- species are related to improved activity, achieving 21.1% VDF selectivity and modest stability for at least 20 h.