A thin orthorhombic LaLuO3 film, grown on SrTiO3 substrate by pulsed laser deposition, is characterized using multi-angle spectral extreme ultraviolet reflectometry (EUVR). Layer structure parameters and optical constants of LaLuO3 are determined simultaneously by fitting angular reflectivity curves in a wide spectral range (70-200 eV). From near-edge optical constant analysis, La: Lu stoichiometry ratio and the film density are derived. Sample structure is additionally analyzed using XRR, AFM and TEM methods. EUVR as a method of structural characterization is discussed in comparison with XRR. Correlation error analysis of the layer structure parameters, obtained from independent EUVR and XRR fits, is presented.