The instability of a falling film under high pressure (droplet formation) was characterized by the dimensionless Reynolds, Weber, and fluid-film numbers and could be predicted in a characteristic diagram. Incipient droplet formation was achieved with the given material properties of the system, i.e., at a constant K-F number, by increasing the volumetric flowrate of the liquid phase. The investigations were performed with the material systems alpha-tocopherol/CO2 and squalane/CO2 in the pressure ranges between 8 and 35 MPa and 6 and 12 MPa, respectively at four different temperatures between 313 and 353 K. The volumetric flowrate of the liquid phase was varied between 10 and 300 ml/min, whereas the speed of the supercritical gas phase in counter-current flow to the falling film in the falling-film cell was kept constant at 7 mm/s. The high-pressure falling-film cell used for this purpose had an external diameter of 104 mm, an internal diameter of 34 mm, and a total length of 710 mm. The diameter and length of the cylindrical falling-film carrier were 10 and 500 mm, respectively.