The spatial decay properties of Wannier functions and related quantities have been investigated using analytical and numerical methods. We find that the form of the decay is a power law times an exponential, with a particular power-law exponent that is universal for each kind of quantity. In one dimension we find an exponent of −3/4 for Wannier functions, −1/2 for the density matrix and for energy matrix elements, and −1/2 or −3/2 for different constructions of non-orthonormal Wannier-like functions.PACS: 71.15. Ap, A growing interest in localized real-space descriptions of the electronic structure of solids has been motivated by the development of computationally efficient "linearscaling" algorithms [1,2] and by the desirability of a local real-space mapping of chemical [3,4] and dielectric [5,6] properties. A primary avenue to such a description is the use of Wannier functions [7][8][9] (WFs), i.e., a set of localized wavefunctions w R (r) obtained from the Bloch functions ψ k (r) by a Fourier-like unitary transformation. A closely related approach is to represent the electronic structure in terms of the density matrix n(r, r ′ ). It is thus not surprising to find considerable recent interest in the localization properties of the WFs [3] and of the density matrix [10,11].In a classic 1959 paper, Kohn proved, for the case of a centrosymmetric crystal in one dimension (1D), that the WFs have an "exponential decay" w(x) ≈ e −hx , where h is the distance of a branch point from the real axis in the complex-k plane [8]. More precisely, lim x→∞ w(x) e qx = 0,The density matrix has a similar decay n(x, x ′ ) ≈ e −h|x−x ′ | . The exponential decay of the WFs has since been proven for the general 1D [12] and single-band 3D[13] cases, and that of the density matrix (more precisely, of the band projection operator) has been proven in general [12]. The energy matrix elements E(R) = w R |H|w 0 , with w R (x) = w(x − R) and R = la a lattice vector, are also expected to have a similar decay,The purpose of this Letter is to address two questions. First, Eq. (1) allows considerable freedom; in fact, it is consistent withfor any exponent α, i.e., a decay which could be faster (α > 0) or slower (α < 0) than pure exponential. Does such a power-law prefactor exist, and if so, what is the exponent α? Second, it has long been understood that relaxation of the orthogonality constraint w 0 |w R = δ 0,R can give "more localized" Wannier-like functions [14][15][16].In what sense are these more localized -a larger h, or a larger α for the same h, or only a smaller prefactor of the tail? We show that the power-law prefactors of Eq. (2) do exist, and that the various quantities have a common inverse decay length h but different exponents α. In 1D we find that α = 3/4 for usual (orthonormal) WFs, α = 1/2 for n(x, x ′ ) and E(R), and α = 1/2 or α = 3/2 for two different constructions of nonorthonormal Wannier-like functions (NWFs). The NWFs of superior decay (∼ x −3/2 e −hx ) can be constructed by a projection method as duals to a set of tria...