Absorption and emission at 4 and 77 K are observed in Cr-doped TiO2 consisting of two sharp no-phonon lines at 12 685 and 12 732 cm-1, and vibronic sidebands with an integrated intensity 104 times that of the no-phonon lines. In undoped TiO2, identical spectra are observed but are a factor of 100 less intense. The center responsible for these spectra is identified as substitutional Cr3+ by observing, in emission, a splitting of the 12 685-cm-1 line of 1.4 cm-1, a value previously determined by EPR measurements. The vibronic sidebands have some structure superposed on a broad band. The vibronics are different in emission and absorption and have a lifetime of 45 μsec, equal to that of the no-phonon line. They are shown to be principally due to defect-induced phonons arising from the Cr3+ defect. We argue that the spectra observed are not characteristic of the usual 2Eg-4A2g transition, and propose that the 4T2 lies lower in energy than the 2Eg state. If so, the new results of this work are (1) no-phonon line emission for the 4T2-4A2 transition and (2) defect phonon states which are different for the 4A2 and 4T2 states. The excitation spectrum is also presented. It shows that the excitation of the Cr3+ emission occurs mainly by the transfer of energy from excited trapping centers rather than by direct excitation.