Polarized x-ray absorption fine structure (XAFS) measurements at the La and Sr sites inLa2−xSrxCuO4(0.075≲x≲0.35)indicate that doped holes introduced with Sr are not uniformly distributed in theCuO2planes but reside in impurity states with the majority of charge located onCuO6octahedra coupled to the Sr dopants by an apical oxygen (denoted as Sr octahedra). A model based on doped hole-induced Jahn Teller (JT) distortions of these Sr octahedra indicates the impurity states are overlapping singlet and triplet ones resulting from pairings of intrinsic and extrinsic holes. The more mobile singlet pairs reside in theCuO2planes, are bound by more than 0.1 eV and could Bose-condense into a superconducting state. The predominant appearance of (mostly) out-of plane triplet states at highxintimately related to the 2D-3D crossover in transport properties and could relate to the observed loss of highTcin the overdoped regime, as confinement of carriers to theCuO2planes is reduced. ©1999 American Institute of Physics.