This article provides a comprehensive review of the synthesis routes and applications of vinylidene (—CH==CH—)-bearing hyfrofluoroolefins (v-HFOs). Currently, among the major routes for synthesizing v-HFOs, such as fluorine-chlorine exchange, isomerization, dehydrohalogenation, selective hydrogenation, hydrodechlorination, and telomerization, the fluorine-chlorine exchange route stands out due to its readily available starting materials and the ease of achieving large-scale production, making it the optimal synthesis route for v-HFOs. Due to the unique molecular structure of v-HFOs, they exhibit excellent heat transfer properties, environmental friendliness, foamability, and etching performance, which are primarily used as refrigerants, heat pump working fluids, cleaning agents, blowing agents, and etching agents. In particular, trans-v-HFOs ((E)-v-HFOs) demonstrate outstanding electrical insulating properties, combined with their excellent heat transfer and cleaning performances, have led to their application in new scenarios such as immersion liquid cooling and charged cleaning. The future development trends of v-HFOs are discussed, including the development of efficient fluorination catalysts, environmentally friendly and green synthetic routes, as well as exploring new applications for v-HFOs.