A systematic study of the thermally induced reaction of 20 transition metals (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, and Cu) with Ge substrates was carried out in order to identify appropriate contact materials in Ge-based microelectronic circuits. Thin metal films, nominally 30 nm thick, were sputter deposited on both amorphous Ge and crystalline Ge(001). Metal-Ge reactions were monitored in situ during ramp anneals at 3 °C s−1 in an atmosphere of purified He using time-resolved x-ray diffraction, diffuse light scattering, and resistance measurements. These analyses allowed the determination of the phase formation sequence for each metal-Ge system and the identification of the most promising candidates—in terms of sheet resistance and surface roughness—for their use as first level interconnections in microelectronic circuits. A first group of metals (Ti, Zr, Hf, V, Nb, and Ta) reacted with Ge only at temperatures well above 450 °C and was prone to oxidation. Another set (Cr, Mo, Mn, Re, Rh, Ru, and Ir) did not form low resistivity phases (<130 μΩ cm) whereas no reaction was observed in the case of W even after annealing at up to 1000 °C. We found that Fe, Co, Ni, Pd, Pt, and Cu were the most interesting candidates for microelectronic applications as they reacted at relatively low temperatures (150–360 °C) to form low resistivity phases (22–129 μΩ cm). Among those, two monogermanides, NiGe and PdGe, exhibited the lowest resistivity values (22–30 μΩ cm) and were stable over the widest temperature window during ramp anneals. In passing, we note that Cu, Ni, and Pd were the most effective in lowering the crystallization temperature of amorphous Ge, by up to 290 °C for our typical ramp anneals at 3 °C s−1.