The kinetics of the thermal decompositions of t-butyl, isopropyl and 2-chloroethyl vinyl ethers into predominantly olefins and acetaldehyde in a seasoned vessel have been studied in a static system. These reactions are homogeneous and essentially unimolecular; they obey first-order kinetics in their early stages. The rate constants are: t-butyl vinyl ether (215–324°), k= 1010·86 exp(–36,184/RT); isopropyl vinyl ether (311·0–375·0°), k= 1012·12 exp(–42,557/RT); 2-chloroethyl vinyl ether (353·0–424·0°), k= 1011·49 exp(–44,752/RT) sec.–1.