The specifics of formation of silver nanoparticles in aqueous solution in the presence of carboxyalkylated amine complexones (NTA and DTPA) have been studied for the first time. Sols with these ligands are found to be formed in alkali solutions at рН ≥ 10.0 and 80°С. Their optical spectra and the particle sizes and morphologies are determined by synthesis conditions: рН, the ratio Ag+/L, and the order of mixing components. A scheme has been suggested for silver nanoparticle formation in the presence of NTA and DTPA, consistent with the experimental results. The efficacy of the prepared silver sols in SERS measurements is shown.