Size-controlled Ag nanoparticles (NPs) were prepared from the decomposition of Ag(I) carboxylates using ethanolamine derivatives as a reducing agent without an additional stabilizing agent. The size of the Ag NPs with a narrow size distribution (sub-10 nm to ca. 40 nm) was controlled precisely by varying the processing parameters, such as the type of reducing agent and the chain length of the carboxylate in the Ag(I) carboxylate. The optical properties, surface composition and crystallinity of the Ag NPs were characterized by ultraviolet-visible spectroscopy, gas chromatography-mass spectrometry, thermal gravimetric analysis, transmission electron microscopy and X-ray diffraction.