Recent progress of the XANES (X-ray absorption near-edge structure) spectral analysis methods for the structure characterization of metal complexes (MC) in solution is reviewed. Typical examples showing the scheme of the apparatus for XAFS (X-ray absorption fine structure) data collection, preparation and handling of solution samples, data treatment and analysis for XANES spectra, and future of XANES spectroscopy are presented. Detailed examples for the apparatus developed for laboratory scale spectrometers for XANES together with a combined spectral analyses using multi scattering method (MS) and molecular orbital (MO) calculation are discussed.