The isobaric binary vapor–liquid equilibrium (VLE) data for the mixture of cumene and acetophenone were studied at 101.3, 30.0, and 10.0 kPa in a modified Rose equilibrium still. This system exhibited no azeotropic behavior at the studied pressures. The consistency of the VLE data was verified by both the Fredenslund test and Redlich–Kister area test. Meanwhile, the experimental data were correlated by the nonrandom two-liquid, universal quasichemical, and Wilson models. The corresponding binary interaction parameters for the three models, which could contribute to the simulation and design for the separation process, were obtained using a maximum likelihood objective function. All three models showed good agreement with the experimental data.