Vapor and liquid equilibrium compositions have been measured for the hexane + 1-hexadecene system at 472.1, 524.7, and 572.5 K and at pressures ranging from 7.9 to 40.1 bar. A continuous-flow apparatus was used both to minimize 1-hexadecene polymerization and to measure the low 1-hexadecene concentrations in the vapor phase. Mixture critical pressures and compositions were measured for the two temperatures above the critical point of hexane. Results with 1-hexadecene are compared with those recently obtained for binary mixtures of hexane with hexadecane and 1-hexadecanol, respectively. The data for these three binary systems have been correlated with the Peng-Robinson equation of state.