The catalyzed reaction of an excess of styrene with n-Bu3GeH using several ruthenium and rhodium complexes gave the corresponding vinylgermanes (alpha-tri-n-butylgermylstyrene, (Z)-beta-tri-12-butylgermylstyrene, and (E)-beta-tri-n-butylgermylstyrene), which are dehydrogenative germylation products. The most effective catalyst was Ru-3(CO)(12) whose use resulted in selective formation of the vinylgermanes in high yields.