Cu K-edge XANES spectroscopy has been used to study local structure around the Cu-site in three-dimensional oxygen deficient perovkite La 8- x Sr x Cu 8 O 20 system. The combination of E//ab and E//c polarization and high resolution XANES spectra on high quality single crystals has allowed us to distinguish the various features associated with the complex Cu-O networks in the system which have then been compared with those of the La 2- x Sr x CuO 4 system.