Local atomic and electronic structure of Dy- and Yb-based dibenzoylmethanide complexes has been investigated by analysis of experimental and theoretical L 3 -edge XANES spectra. The local atomic structure similarity between recrystallized and as-synthesized samples has been proved by XANES. Differences in the experimental XANES spectra collected for a Ln-complexes with a different ligand ratio (dbm - ): (O-btd - ) have been observed and assigned with a higher abundancy of elongated Ln-N bonds with respect to Ln-O for the sample where Ln-ions coordinated by higher number of O-btd - ligands. In this work we also critically discussed XANES simulations based on monoelectronic approach as implemented in FDMNES code for L 3 -edge spectra calculated for Ln-complexes. Density of electronic state calculation has been performed in order to elucidate the origin of the XANES features. Since the product yield of as-synthesized Ln-complexes is significantly higher rather than after re-crystallization this work demonstrate a high potential of DFT-assisted XANES analysis for the structural investigation of as-synthesized complexes without long-range atomic ordering.