Thermodynamics of isomerization reactions on some substituted vinyl methyl ethers have been studied for evaluating the magnitudes of the interaction energies S [R1... R2] between the substituents R1 and R2, juxtaposed in a cis position across the C C bond of vinyl ethers. The results obtained are (values given in kJ mol-1): S [Me... t-Bu]= 18.2±1.0, S [Ph... i- Pr]= 11±2, S [i-Pr... Et]= 6.1±0.6, S [i-Pr... i-Pr]= 6.0±0.6, S [0... t-Bu]= 2.9±0.5, S [O... i-Pr]=- ...