The droplet undercooling prior to crystallization during containerless processing in a drop tube is calculated on the basis of nucleation theory and processing parameters. The influences of droplet size, wetting angle, and cooling rate on undercooling are also evaluated under the situation of heterogeneous nucleation. An experimental study of containerless solidification is performed on Ag28.1 Cu41.4 Ge30.5 teary alloy in comparison with the theoretical analysis. It is revealed that, in the case of heterogeneous catalysis, the droplet size is only an ostensible parameter to influence undercooling, whereas the wetting angle is the essentially dominating factor. The different cooling rates in such a case also have an effect on droplet undercooling, but this effect is not significant. The calculated results will agree well with the experimental data if the inverse relationship between wetting angle and droplet size is given.