Abstract We present a set of ultramassive white dwarf models, focused on masses above 1.3 M ⊙. Given the uncertainties about the formation and compositions of such objects, we construct parameterized model sequences, guided by evolutionary calculations including both single star and double white dwarf merger formation channels. We demonstrate that the cooling of objects with central densities in excess of 109 g cm−3 is dominated by neutrino cooling via the Urca process in the first ≈100 Myr after formation. Our models indicate that the recently discovered ultramassive white dwarf ZTF J190132.9+145808.7 is likely to have experienced this Urca-dominated cooling regime. We also show that the high densities imply that diffusion is unlikely to significantly alter the core compositions of these objects before they crystallize.