The (hydroxyalkenyl) germanes (E)-Et3GeCH CHC (OH) R2 (R= Me, Ph) are prepared in a catalytic and stoichiometric manner by addition of HGeEt3 to the alkynols HC⋮ CC (OH) R2 in the presence of Rh (acac)(cyclooctene)(PCy3). The complexes Rh (acac){η2-(E)- Et3GeCH CHC (OH) R2}(R= Me, Ph) play the most important role during these processes.