Germanium is one of the most significant semiconductors to be used for electronic devices due to small bandgap and high intrinsic mobility of holes and electrons. Germanium has received a large attention due to its extraordinary reactivity and properties. It is commonly used in fluorescent lamps and as catalyst as well to produce various types of plastic. Germanium nanomaterials have broad range of applications from photovoltaic devices to phase-change memory materials. Germanium forms complexes by reacting with numerous elements such as carbon, oxygen, nitrogen, hydrogen, and phosphorous as a part of several organic compounds. Germanium coordinates with these elements by single, double, and triple linkages. Interestingly, all such reactions occur at ambient temperature usually in tetrahydrofuran under vacuum. Germanium may also react directly with primary and secondary nitrogen in the presence of a suitable base, whereas with tertiary nitrogen, it may react directly even in the absence of a base. Nevertheless, this chapter describes the modern techniques in synthesis of organometallic compounds of germanium.