Binding energies and wave functions of inner-shell electronic states in superheavy quasimolecules with (Zp+Zt)α>1 are calculated. Ionization during a collision of very heavy ions is investigated within a molecular basis generated by the solutions of the two-center Dirac equation. Transitions to vacant bound states as well as direct excitation to the continuum are taken into account. We present theoretical values for the ionization probability as a function of impact parameter, bombarding energy, and combined nuclear charge. Our computed results are compared with recent experimental data. It is suggested that relativistic binding energies of electrons in superheavy quasimolecules can be determined experimentally via the impact-parameter dependence of ionization and the anisotropy of quasimolecular radiation.