The formation of a spin glass usually requires both structural disorder and frustrated magnetic interactions. Consequently, the origin of spin-glass behaviour in Y2Mo2O7-in which magnetic Mo 4+ ions occupy a frustrated pyrochlore lattice with minimal compositional disorder-has been a longstanding question. Here, we use neutron and X-ray pair-distribution function (PDF) analysis to develop a disorder model that resolves apparent incompatibilities between previously-reported PDF, EXAFS and NMR studies and provides a new and physical mechanism for spin-glass formation. We show that Mo 4+ ions displace according to a local "2-in/2-out" rule on each Mo4 tetrahedron, driven by orbital dimerisation of Jahn-Teller active Mo 4+ ions. Long-range orbital order is prevented by the macroscopic degeneracy of dimer coverings permitted by the pyrochlore lattice. Cooperative O 2− displacements yield a distribution of Mo-O-Mo angles, which in turn introduces disorder into magnetic interactions. Our study demonstrates experimentally how frustration of atomic displacements can assume the role of compositional disorder in driving a spin-glass transition. PACS numbers: 75.50.Lk,61.05.fm,75.10.Nr,75.25.Dk In a spin-glass transition, spins freeze into a metastable arrangement without long-range order [1]. It is generally accepted that two conditions must be satisfied for a spin-glass transition to occur: interactions between spins must be disordered and these interactions must also be frustrated [2,3]. In canonical spin glasses-e.g., dilute magnetic alloys such as Cu 1−x Mn x [4] and site-disordered crystals such as Fe 2 TiO 5 [5]-the nature of structural disorder and its coupling to magnetism is well understood. However, spin-glass behaviour is also observed in well-ordered crystals where the geometry of the magnetic lattice alone can generate frustration (see, e.g., [6][7][8]). Here, the mechanism of spin-glass formation poses an important challenge for theory [9,10]. The prototypical material that shows this anomalous behaviour is Y 2 Mo 2 O 7 -a system with apparently unremarkable levels of structural disorder, but with thermodynamic properties indistinguishable from canonical spin glasses (for a review, see [11]).The structure and dynamics of Y 2 Mo 2 O 7 have been extensively studied. The conventional nature of the spin-glass transition (freezing temperature T f = 22 K [12]) has been shown by exhaustive thermodynamic measurements, including non-linear susceptibility [12,13], specific heat [14,15], a.c. susceptibility [16], and thermo-remanent magnetization [17][18][19]. Inelastic neutron scattering [20], muon-spin rotation (µSR) [21], and neutron spin-echo studies [22,23] reveal a reduction in the spin-relaxation rate as T f is traversed. Neutron diffraction measurements show that the average structure is well-described by the ordered pyrochlore model (space group F d3m) both below and above T f [24,25]. In this structure, the average positions of magnetic Mo 4+ ions describe a network of corner-sharing tetrahedra [ Fig. 1 coo...