In this work we present a study of the ferroelectric switching kinetic process in strontium–barium niobate (SBN). The kinetics of polarization deduced from the dynamics of the diffuse second harmonic generation is in good qualitative agreement with thekinetics observed by more traditional polarization methods. Our work highlights the specific characteristics of polarization reversal in SBN, which is fundamentally different from that which occurs in model ferroelectrics. The presented optical measurements of the polarization processes provide several experimental advantages over traditional electrical measurements. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)