We present general guidelines for finding solid-state systems that could serve as coherent electron-spin-photon interfaces even at relatively high temperatures, where phonons are abundant but cooling is easier, and show that transition-metal ions in various crystals could comply with these guidelines. As an illustrative example, we focus on divalent nickel ions in magnesium oxide. We perform electron-spin-resonance spectroscopy and polarization-sensitive magneto-optical fluorescence spectroscopy of a dense ensemble of these ions and find that (i) the ground-state electron spin stays coherent at liquid-helium temperatures for several microseconds and (ii) there exist energetically well-isolated excited states that can couple to two ground-state spin sublevels via optical transitions of orthogonal polarizations. The latter implies that fast coherent optical control over the electron spin is possible. We then propose schemes for optical initialization and control of the ground-state electron spin using polarized optical pulses, as well as two schemes for implementing a noise-free broadband quantum optical memory at near-telecom wavelengths in this material system.