We study the formation of Rydberg atoms in expanding plasmas at temperatures of 1-1000 K and densities from 10(5)-10(10) cm(-3). Up to 20% of the initially free charges recombine in about 100 micros, and the binding energy of the Rydberg atoms approximately equals the increase in the kinetic energy of the remaining free electrons. Three-body recombination is expected to dominate in this regime, yet most of our results are inconsistent with this mechanism.