Vapor-liquid equilibria in systems with polar molecules tend to show a rather complex phase behavior. In order to investigate the phase boundaries in mixtures of dipolar and quadrupolar components five binary systems of the components R 22, R 23, CO2 and CS2 have been selected. Experimental VLE data for the systems R 22-R 23, R 22-CO2, CS2-R 22, R 23-CO2 and CS2-R 23 are reported in this paper at temperatures between 254 and 473 K and pressures up to 25 MPa. The data were correlated with one empirical and one semi-empirical equation of state.