The research presented contributes to the global goal of responsible production by providing robust tools for the optimization of gold dissolution in cyanide-free gold leaching solutions, which represent emerging non-toxic gold technologies. In the current study, gold dissolution was investigated in ferric and cupric chloride solutions. The effect of the redox potential on the open circuit potential (OCP) and dissolution rate of gold was investigated experimentally in the parameter range of T = 25–95 °C, [Fe3+/Cu2+] = 0.02–1.0 M, [Cl−] = 1–5 M, pH = 0.0–2.0, and ωcyc = 2500 RPM. A high rotational speed was chosen to minimize the effects of limited mass transfer rate. The aim was to provide tools for estimating the gold dissolution rate in ferric and cupric chloride solutions, using the solution properties. The results showed that redox potentials, OCPs, and dissolution rates were constantly higher in ferric chloride solutions compared to corresponding cupric chloride solutions. The multilinear regression models for redox potential showed that a rise in temperature and oxidant concentration increased the redox potential in both ferric and cupric chloride solutions. However, an increase in the chloride concentration decreased the redox potential in ferric chloride solutions, whereas the effect was the opposite in cupric solutions. A rise in the pH value increased the redox potential in ferric solutions, but this was found to be an insignificant variable in cupric chloride leaching within the investigated parameter range. The redox potential had a positive correlation with OCP and the logarithm of the gold dissolution rate in both investigated systems. The results suggest that, in the chloride leaching systems examined, the solution properties can be used to determine the redox potential, and furthermore, the redox potential can be used to estimate the gold dissolution rate. This study provides an experimentally verified tool for the robust estimation of the gold dissolution rate in chloride systems.