The process of growing large diameter single crystals of Al2O3:Ti3+by vertical solidification of the melt is described, and some of the problems in producing high‐optical quality material are discussed. The characterization of the distribution and valance state of titanium ions was performed by x‐ray techniques and laser Raman microprobe methods. The presence of other impurity ions, specifically iron, was also determined. In some cases titanium was found in the grown crystal to be in the rutile form. In addition, Ti‐Fe pairs, and concentrated regions of titanium on the surface of the boule were also observed. Some procedures for minimizing these problems are discussed. The results of optical absorption, fluorescence, and lifetime measurements are reported. The addition of Fe is shown to produce a broad absorption band in the red region of the spectrum, and two‐photon laser excitation terminating in the ultraviolet spectral region produces a broad blue emission band.