We propose models of Dark Matter that account for the 511 keV photon emission from the Galactic Centre, compatibly with experimental constraints and theoretical consistency, and where the relic abundance is achieved via p-wave annihilations or, in inelastic models, via co-annihilations. Due to the Dark Matter component that is inevitably upscattered by the Sun, these models generically predict keV electron recoils at detectors on Earth, and could naturally explain the excess recently reported by the XENON1T collaboration. The very small number of free parameters make these ideas testable by detectors like XENONnT and Panda-X, by accelerators like NA64 and LDMX, and by cosmological surveys like the Simons observatory and CMB-S4. As a byproduct of our study, we recast NA64 limits on invisibly decaying dark photons to other particles.