A new approach was developed to control the size of gold nanoparticles in citrate reduction by altering the concentration of chloride ions. The size of the as-prepared gold nanoparticles could be tuned in the range 19-47 nm at a specific molar ratio of citrate and tetrachloroauric acid (5:1) by simply changing the concentration of chloride ions from 0 to 20 mM. UV-visible spectra and TEM observations showed that the increased size of the gold particles was primarily related to the promoted aggregation of the primary gold particles. The aggregation was attributed to their decreased surface charge as the chloride ion concentration in the reaction solutions increased. This approach could also be extended to other reaction systems, for example, the size of gold nanoparticles prepared by NaBH(4) reduction increased from 3 to 12 nm as the chloride ion concentration was increased from 0 to 20 mM.