The development of a critical crevice solution plays an important role in crevice corrosion propagation in nickel alloy 625. In this investigation, the polarization response of alloy 625 in a set of simulated crevice chemistries using metal chloride salts has been studied. Specifically, solutions were made from NiCl2, CrCl3, FeCl2, MoCl3, and NbCl5 in the same stoichiometric ratio as they appear in the alloy and ranging in concentration from 3.0 to 5.0 molal (m). It was found that Mo and Nb contributed to lower open circuit potentials (OCP) and increased critical peak current densities (i.e. activation). Solutions that substituted NiCl2 for MoCl3 and NbCl5, such that the chloride content was equivalent to that of the NiCrFeMoNb solution, presented high OCP values and passive behavior. To better understand the polarization data, solution speciation and pH were calculated using a commercially available software package. It was found that for concentrations ranging from 3.0 to 5.0 m, the pH values were on the order of −1.0. In addition, the active to passive transition appeared to correlate with an increase of Mo3+ concentration in solution. For comparison, the polarization response of alloy 625 in HCl-based solutions was investigated. Over the range of HCl concentrations studied, the critical peak current densities were typically lower than the metal salt solutions at equivalent calculated pH. In addition, an equation for preparing HCl solutions at the needed pH to obtain an equivalent critical peak current density as observed in the NiCrFeMoNb solutions is presented.