Double Rydberg states were populated by triple electron capture in col
lisions of highly charged ions with atoms. The highest stabilization o
f states produced by triple capture at upsilon congruent to 0.2 a.u. w
as found for binding energies of the projectile electrons near the lim
its of the (2,n,n') and (3,n,n') series. Population of triply excited
double Rydberg states was confirmed by the emission of Rydberg transit
ions. Results are interpreted by two successive autotransfer into Rydb
erg states for (3,n,n') states and of one-step two-electron autotransf
er for (2,n,n') states.