Electron paramagnetic resonance study of congruent LiNbO3 single crystal weakly doped (0.1 wt%) with erbium is reported. The EPR lines originating both from the 167Er isotope with a hyperfine structure, as well as from the evenEr isotopes causing fine structure, are identified. Angular dependence of the EPR lines reveals the presence of several non‐equivalent centers. Deconvolution of the EPR line into several Lorentzian components in a plane perpendicular to the z‐axis (optical c‐axis) allowed us to show the Er3+ center with the lowest (C1) point group symmetry and estimate the values of g‐tensor. The obtained results confirmed the model of non‐ equivalent centers of the rare‐earth ions in lithium niobate having the lowest C1 symmetry due to the presence of intrinsic defects in the near‐neighborhood of RE3+. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)