Abstract Dithia-and dioxa-germoles: R 2 Ge-X-CR′= CR′-X (X= S, O), have been prepared from diorganodihalogermanes and R′(NaS) C= C (SNa) R′, 1, 2- benzenedithiol, α-hydroxy ketones, R “(KO) C= C (OK) R” or dioxastannole and by cleavage of Ge-N bonds of diorganobis (diethylamino) germanes by benzoin. The synthesis of spirobidithiagermoles is also reported.