Scatterometry is frequently used as a non-imaging indirect optical method to reconstruct the critical dimensions (CD) of periodic nanostructures. A particular promising direction is EUV scatterometry with wavelengths in the range of 13 - 14 nm. The conventional approach to determine CDs is the minimization of a least squares function (LSQ). In this paper, we introduce an alternative method based on the maximum likelihood estimation (MLE) that determines the statistical error model parameters directly from measurement data. By using simulation data, we show that the MLE method is able to correct the systematic errors present in LSQ results and improves the accuracy of scatterometry. In a second step, the MLE approach is applied to measurement data from both extreme ultraviolet (EUV) and deep ultraviolet (DUV) scatterometry. Using MLE removes the systematic disagreement of EUV with other methods such as scanning electron microscopy and gives consistent results for DUV.