The thesis focuses on the syntheses, structural characterizations and chemical bonding analyses for several ternary R–M–Ge (R = rare earth metal; M = another metal) intermetallics. The challenges in understanding the main interactions governing the chemistry of these compounds, which lead to our inability to predict their formation, structure and properties, are what provided the motivation for this study. In particular, the R2MGe6 (M = Li, Mg, Al, Cu, Zn, Pd, Ag), R4MGe10-x (M = Li, Mg), R2Pd3Ge5, Lu5Pd4Ge8, Lu3Pd4Ge4 and Yb2PdGe3 phases were synthesized and structurally characterized. Much effort was put into the stabilization of metastable phases, employing the innovative metal flux method, and into the accurate structure solution of twinned crystals. Cutting-edge position-space chemical bonding techniques were combined with newmethodologies conceived to correctly describe the Ge–M, Ge–La and also La–M polar-covalent interactions for the La2MGe6 (M = Li, Mg, Al, Cu, Zn, Pd, Ag) series. The present results constitute a step forward in our comprehension of ternary germanide chemistry as well as providing a good playground for further investigations.