Mueller matrix ellipsometry (MME) is applied to characterize lithographic patterns with natural line edge roughness (LER). A computationally efficient approach based on effective medium approximation is proposed to model the effects of LER in MME measurements. We present both the theoretical and experimental results on lithographic patterns with realistic LER which demonstrate that MME in combination with the proposed effective modeling method is capable of quantifying LER amplitudes. Quantitative comparisons between the MME and scanning electron microscopy measured results also reveal the strong potential of this technique for in-line nondestructive line roughness monitoring. (C) 2015 Elsevier B.V. All rights reserved.