Copper nanoparticles with different particle sizes were prepared by a wet chemical reduction method in the presence of organic modifiers, such as citric acid (CA), hexadecyl trimethyl ammonium bromide, Tween-80 (Tween), and polyethylene glycol 6000. Selective oxidation of sustainable 1,2-propanediol with O2 to high-valued lactic, formic, and acetic acids catalyzed by the copper nanoparticles in an alkaline medium was investigated. The small-sized CuCA nanoparticles with the average particle size of 15.2 nm favored the formation of acetic and formic acids while the CuTween nanoparticles with the average particle size of 26.9 nm were beneficial to the formation of lactic acid. The size effect of copper nanoparticles on the catalytic oxidation of 1,2-propanediol to the carboxylic acids was obvious.