Solvent effects on the microwave-assisted synthesis of germanium nanoparticles are presented. A mixture of oleylamine and 1-dodecene was used as the reaction solvent. Oleylamine serves as a reducing agent in the synthesis while both molecules act as binding ligands. Increased concentrations of 1-dodecene in the solvent mixture were found to increase the size of the formed nanoparticles. Crystallinity was also dependent on the solvent mixture. Amorphous nanoparticles were obtained at lower 1-dodecene concentrations, whereas, at higher concentrations, particles contained crystalline and amorphous domains. 11-Methoxyundec-1-ene was synthesized to replace 1-dodecene in the reaction mixture for nuclear magnetic resonance (NMR) studies. 1H NMR of the reaction products shows that both solvent molecules in the system act as binding ligands on the nanoparticle surface. Nanoparticles were characterized using powder X-ray diffraction, scanning transmission electron microscopy, and spectroscopy techniques (Raman, UV-vis, FT-IR, and NMR).