Structural iron in smectites correlates with the cell edge length b and increases the refractive index. The cell edge length b is usually obtained from the position of the (060) reflection, but in this work we show that such b values differ from the values obtained from Rietveld fits because contributions from (hkl) reflections shift the position of the (060) reflection. The correlation between Fe and cell edge length b was significant (r2 > 0.99); the relationship is b [A Å] = 8.9977(0.0035) + 0.1117(0.0032)×Fetot. Furthermore, we present for the first time measurements of the refractive index n of Fe-bearing smectites, applying a recently published turbidity method (Weidler & Friedrich, 2007). The refractive index correlates both with structural iron (r2 = 0.64) and with b (r2 = 0.94).