We investigate electron-ion recombination in nanoplasmas produced by the ionization of rare-gas clusters with intense femtosecond extreme-ultraviolet (XUV) pulses. The relaxation dynamics following XUV irradiation is studied using time-delayed 790-nm pulses, revealing the generation of a large number of excited atoms resulting from electron-ion recombination. In medium-sized Ar-Xe clusters, these atoms are preferentially created in the Xe core within 10 ps after the cluster ionization. The ionization of excited atoms serves as a sensitive probe for monitoring the cluster expansion dynamics up to the ns time scale.