The density and isobaric phase equilibria of the binary system methylcyclopentane + ethyl acetate were investigated for the first time in this work. The density of the system was measured at 101 kPa from 288.15 to 308.15 K for the entire composition range thanks to a vibrating tube densimeter. Positive excess molar volumes were observed and correlated by using a Redlich−Kister equation. New isobaric vapor−liquid equilibrium data for the system methylcyclopentane + ethyl acetate were measured by means of a recirculation ebulliometer. The phase equilibrium was measured at 25, 50, and 101.3 kPa. Equilibrium compositions were determined indirectly from density measurements of the liquid and condensed vapor phases. Some additional density and vapor−liquid equilibrium data measurements for the binary system ethyl acetate + methylcyclohexane were performed for comparison with previously published results and validation of the experimental protocol. The methylcyclopentane + ethyl acetate binary mixture displays pronounced positive deviations from ideality and a positive azeotrope. Three thermodynamic consistency tests were employed to validate the produced data set. The reported data were successfully correlated by the NRTL model, and the modified UNIFAC predictive model was also used. UNIFAC provides a very good description of the phase behavior at 101.3 kPa, whereas predictions are less accurate at low pressures (25 and 50 kPa).