We study the zero-temperature phase diagram of a dissipationless and disorder-free Josephson junction chain. Namely, we determine the critical Josephson energy below which the chain becomes insulating, as a function of the ratio of two capacitances: the capacitance of each Josephson junction and the capacitance between each superconducting island and the ground. We develop an imaginarytime path integral Quantum Monte-Carlo algorithm in the charge representation, which enables us to efficiently handle the electrostatic part of the chain Hamiltonian. We find that a large part of the phase diagram is determined by anharmonic corrections which are not captured by the standard Kosterlitz-Thouless renormalization group description of the transition.