We consider the Dicke Hamiltonian, a simple quantum-optical model which exhibits a zerotemperature quantum phase transition. We present numerical results demonstrating that at this transition the system changes from being quasi-integrable to quantum chaotic. By deriving an exact solution in the thermodynamic limit we relate this phenomenon to a localisation-delocalisation transition in which a macroscopic superposition is generated. We also describe the classical analogues of this behaviour.At zero temperature, systems of N interacting particles can exhibit a quantum phase transition (QPT) as a function of a coupling parameter λ in the limit that N → ∞. How do the precursors of such a transition influence quantum chaotic (and non-chaotic) behaviour of the same system for finite N ?One of the most direct indicators of the emergence of quantum chaos is the change in energy level spacing statistics from Poissonian to being described by the Gaussian ensembles of Random Matrix Theory. Although this change-over has been observed in many systems [1,2,3,4], only in a comparatively few, isolated cases has the onset of quantum chaos been correlated with the presence of a QPT. Important examples include spin glass shards, which have recently been used in modeling the onset of chaos in quantum computers [5], the Lipkin model [6], the interacting boson model [7], and the three-dimensional Anderson model [8,9], where the change in level statistics occurs at the metalinsulator (localisation-delocalisation) transition found in disordered electronic systems.In this Letter we consider the Dicke Hamiltonian (DH) [10], a quantum-optical model describing the interaction of N two-level atoms with a number of bosonic modes. We demonstrate that a crossover between Poisson and Wigner-Dyson statistics in this model for finite N is intimately connected to a mean-field type superradiance QPT.The simplicity and generality of the Dicke Hamiltonian have afforded it appeal both for the investigation of quantum chaos, and as a model for phase transitions at a critical coupling λ c induced by the interaction with light. The level statistics for finite N have revealed the existence of quantum chaos in certain isolated regimes of the model [11,12]. On the other hand, the QPT aspect for N → ∞ has been discussed in the context of superradiance [13,14], and recently for exciton condensation [15]. Here, we derive an exact solution for all eigenstates, eigenvalues and critical exponents in the thermodynamic limit, and show that above the critical point λ = λ c the ground-state wavefunction bifurcates into a macroscopic superposition for any N < ∞. Our numerical results indicate that a localisation-delocalisation transition for N → ∞ underlies the cross-over between Poissonian and Wigner level-spacing distributions for finite N . Furthermore, we use an exact Holstein-Primakoff transformation to derive the classical limit of the model for arbitrary N and find a transition at λ = λ c from regular to chaotic trajectories. The latter are delocalised around ...