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High quality γ-BiB 3 O 6 single crystals up to 16 × 18 × 32 mm 3 in size were grown by the Kyropoulos technique. Indexes of the faces for as grown γ-BiB 3 O 6 single crystals were determined, and transmission spectra were recorded in polarized light. The band gap was found to be E g = 3.982, 3.968, and 4.008 eV at 300 K for E∥a, b, and c, respectively. E g decreases linearly versus temperature with a dE g /dT = 0.00127 eV/deg rate for E∥a as temperature grows from 80 to 300 K. Photoluminescence in the broad 2.5 eV band, which is excited in a band near the fundamental absorption edge and quenches completely at 250 K, is associated with self-trapped excitons.

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