The Turkevich–Frens synthesis starting conditions are expanded, ranging the gold salt concentrations up to 2 mM and citrate/gold(III) molar ratios up to 18:1. For each concentration of the initial gold salt solution, the citrate/gold(III) molar ratios are systematically varied from 2:1 to 18:1 and both the size and size distribution of the resulting gold nanoparticles are compared. This study reveals a different nanoparticle size evolution for gold salt solutions ranging below 0.8 mM compared to the case of gold salt solutions above 0.8 mM. In the case of [Au3+] < 0.8 mM, both the size and size distribution vary substantially with the citrate/gold(III) ratio, both displaying plateaux that evolve inversely to [Au3+] at larger ratios. Conversely, for [Au3+] ≥ 0.8 mM, the size and size distribution of the synthesized gold nanoparticles continuously rise as the citrate/gold(III) ratio is increased. A starting gold salt concentration of 0.6 mM leads to the formation of the most monodisperse gold nanoparticles (polydispersity index < 0.1) for a wide range of citrate/gold(III) molar ratios (from 4:1 to 18:1). Via a model for the formation of gold nanoparticles by the citrate method, the experimental trends in size could be qualitatively predicted: the simulations showed that the destabilizing effect of increased electrolyte concentration at high initial [Au3+] is compensated by a slight increase in zeta potential of gold nanoparticles to produce concentrated dispersion of gold nanoparticles of small sizes.