The direct C-H germylation of heteroarenes, arenes, and benzylic C-H bonds promoted by lithium tetramethylpiperidide (LiTMP) is reported. The method is rapid, selective, and operationally simple, consisting of direct addition of all reagents at room temperature (one-pot procedure). The synthetic utility of these newly accessed aryl germanes as viable coupling partners in Pd catalysis is also showcased.