The phase behavior of the carbon dioxide + cycloheptane binary system for which no literature data are available has been examined at temperatures ranging from 292.6 to 372.8 K. Saturation pressures, ranging from 23.9 to 154.8 bar, were acquired by a synthetic and visual method. In concrete terms, an adjustable-volume high-pressure cell was utilized to measure bubble and dew point pressures by visual detection of phase transitions at constant overall composition. A total of 11 different mixtures with mole fractions of carbon dioxide ranging from 0.20 to 0.96 were prepared, and a total of 99 experimental points were reported. The experimental results obtained in this work reveal the absence of liquid–liquid immiscibility in the studied temperature range and make it possible to conclude that the vapor–liquid critical line of the binary system is continuous and uninterrupted between the two pure compounds. Experimental data were correlated with the Peng–Robinson equation of state and classical van der Waals mixing rules with temperature-dependent binary interaction parameters. They were also compared to the PPR78 model, an entirely predictive group contribution method in which the kij depends on temperature.