The kinetic instability of iron(III) thiocyanate complexes in aqueous solution, evidenced by the loss of solution colour with time, has made it difficult to determine reliable equilibrium data. A technique, which measures the absorbance of these solutions as a function of time within milliseconds of mixing Fe³⁺ with SCN^- and which extrapolates to an initial spectrum at time zero, has been designed to overcome these difficulties and is described in this paper. Two complexes, Fe(SCN)²⁺ and Fe(SCN)₂⁺, have been identified upon analysing the absorbance data for thiocyanate concentrations up to 0.25 M at 25^oC and an ionic strength of 0.5 M. Equilibrium constants, K₁ = and K₂ = have been determined and comparisons made with the literature.