Isothermal vapor-liquid equilibrium data for the six following asymmetric binary systems were measured: ethane + decane at 411 and 444 K, propane + dodecane at 419 and 458 K, propane + 1-decanol at 408 and 448 K, ethane + 1-decanol at 448 K, ethylene + 1-decanol at 308 and 318 K, and carbon dioxide + dodecane at 318 K. A static apparatus equipped with rapid on-line sampler-injectors (ROLSIs) was used. With this device, very small samples can be withdrawn from the vapor and liquid phases in the equilibrium cell and transferred directly into the carrier gas stream for gas chromatographic analysis. The experimental data are compared to literature data and to the results predicted with the PSRK group contribution equation of state.