[reaction: see text]In the photochemical bis-germylation of C60 with 1,1,2,2-tetrakis(2,6-diethylphenyl)-1,2-digermirane (1), a cycloadduct (2) is obtained in high yield for the first time. Spectroscopic analysis and theoretical investigation confirm that 2 (which has C1 symmetry) results from 1,4-cycloaddition. Control experiments and laser flash photolysis experiments suggest that an exciplex intermediate is responsible for the formation of 2. The redox properties of 2 were examined by differential pulse voltammetry.