The first industrial manufacture of vinyl acetate involved addition of acetic acid to acetylene in the gas phase over Zn(OAc)₂/charcoal at 170-250 °C:

At a 60-70% acetylene conversion. the selectivity to vinyl acetate reaches 93%  (based on C₂H₂) and 99%  (based on AcOH). For a time, Hg(OAc)₂ and Zn silicate were also used as catalysts. Although thesc proccrscs are distinguished by high selectivities, simple reaction control, and insignificant catalyst costs, the lower ethylene cost couplcd with its storage and transport capability has plagued the acetylene route. However, several vinyl acctate plants based on acetylene in Western and Eastern Europe havc been able to maintain their processes. In 1994, 9%  of the vinyl acetate production in Western Europe, Eastern Europe, and Asia was still based on acetylcne. In the USA, all acctylcne-based plants have been shut down.