VLE data for binary systems of methanol (1)+cyclopentyl methyl ether (2) were measured at five equalspaced temperatures between 313.15 and 353.15 K using a circulation-type equilibrium apparatus with on-line gas chromatography analysis. This binary system shows strong positive deviation from Raoult’s law and forms an azeotrope at each temperature. The experimental data were correlated with the Peng-Robinson equation of state using the Wong-Sandler mixing rule combined with the NRTL excess Gibbs free energy model. The overall average relative deviations of pressure (ARD-P (%)) and vapor phase compositions (ARD-y (%)) between experimental and calculated values through the temperature range from 313.15 to 353.15 K were 0.298 and 0.499%, respectively. In the range of experimental temperature, azeotropic compositions showed a linear relationship with temperature and were correlated by the empirical equation of xazeo=0.001 T/K+0.617.