A study of the topographical changes of Li/Si(lll) during annealing has been conducted using a high-temperature scanning tunneling microscope. Depending on the Li coverage and postdeposition annealing temperature the surface exhibited a variety of structures replacing the initial (7x7) reconstruction during in situ investigations. In addition to the previously observed (3x1) structure a coexistence phase with domains of(nxn) (n = 5,7,9), a (4x4) structure, and a faceting transition were imaged. Distinct differences were noticed on the Li/Si(111)-(3x1) surface compared to the corresponding Na structure. Moreover, the dynamic properties of the morphological transformations were revealed by a high-temperature scanning tunneling microscope.