Enriched Fe isotope tracer studies demonstrate that aqueous Fe(II) undergoes electron transfer and atom exchange with goethite. Such processes influence contaminant fate and trace-element mobility, and result in stable Fe isotope fractionation in both biological and abiological processes. To date, the majority of experimental studies of aqueous Fe(II) and Fe oxide interactions have been done at circumneutral pH. The effect of pH variations on the rate and extent of Fe isotope exchange between aqueous Fe(II) and iron oxide minerals, as well as the natural mass-dependent fractionation between these species, has not been adequately explored. Here, the three-isotope method (57Fe–56Fe–54Fe), using an enriched 57Fe tracer, was used to investigate the effect of pH (between 2.5 and 7.5) on the rate and extent of isotopic exchange. 56Fe/54Fe ratios were used to determine the natural, mass-dependent stable isotope fractionation, between aqueous Fe(II) and goethite. Three Fe(II) solutions differing in their initial 56Fe/54Fe ratios were used to approach isotopic equilibrium from multiple directions. The 57Fe-enriched tracer data indicate that the extent of isotopic exchange between Fe(II)aq and goethite was positively correlated with pH, where the least amount of exchange occurred at the lowest pH. Similarly, initial kinetic isotope fractionations were influenced by pH; at low pH, minimal kinetic isotope effects were observed relative to large effects at high pH, suggesting a relation between the extent of sorbed Fe(II) and kinetic isotope effects. Continued exchange over time at high pH, however, erases the initial kinetic isotope effects, and the system fundamentally reached isotopic equilibrium by the end of the experiment. Our results show that the interplay between kinetic and equilibrium effects may prevent confident extrapolation to infer equilibrium fractionation factors when only small amounts of Fe exchange occur.