Several extended Rydberg series have been experimentally identified in triply excited states of hollow lithium, by use of electron spectrometry and synchrotron radiation at the Advanced Light Source. Energies, partial cross sections, and quantum defects have also been calculated using the R-matrix approximation. Our results show that the two inner electrons stay in a core-excited state of given symmetry while the behavior of the third electron is mostly governed by the nuclear potential screened by the two inner electrons.