Isothermal vapor-liquid equilibrium (VLE) data for the perfluoromethyl vinyl ether + chlorotrifluoroethylene system were measured in a vapor-liquid equilibrium still with a vapor recycling system at four temperatures from (267.67 to 282.62) K. The uncertainty of the temperature was +/- 0.01 K, and the accuracy of the pressure was +/- 0.05 %. The experimental data were correlated with the NRTL equation and the Wilson equation. The calculated results agree well with the experimental data. Azeotropic VLE behaviors can be observed at certain compositions from the experimental data.