AbstractStudies of mixed mobile phases in supercritical fluid chromatography must include consideration of a number of factors. Phase equilibria and critical parameters of a mixed fluid are very important in both the solvent delivery system and in the chromatographic column. The effects of pressure and temperature on retention with mixed mobile phases were studied and compared to estimated density values. System equilibration times with regard to pressure, temperature, and composition were studied. A mixed mobile phase was applied to the analysis of a high‐molecular‐weight metalloporphy