Recent measurements by Hipparcos present observational evidence supporting the existence of some white dwarf (WD) stars with iron-rich core composition. In connection with this, the present paper is aimed at exploring the structure and evolution of iron-core WDs by means of a detailed and updated evolutionary code. In particular, we examined the evolution of the central conditions, neutrino luminosity, surface gravity, crystallization, internal luminosity profile and ages. We find that the evolution of iron-rich WDs is markedly different from that of their carbon-oxygen counterparts. In particular, cooling is strongly accelerated (up to a factor of 5 for models with pure iron composition) as compared with the standard case. Thus, if iron WDs were very numerous, some of them would have had time enough to evolve at lower luminosities than that corresponding to the fall-off in the observed WD luminosity function.