Single crystals of two new metal tellurates Bi MTeO ( M = Al, Ga) with a honeycomb layered structure were obtained by the molten flux method and characterized. The Bi MTeO compounds both crystallize into a non-centrosymmetric trigonal space group of P312 (no. 149) with cell parameters of a = 5.0667(8) Å, c = 4.9920(16) Å and a = 5.107(3) Å, c = 4.932(6) Å, respectively. The non-centrosymmetry of BiAlTeO and BiGaTeO originates from the packing order of the octahedra. In these two structures, TeO octahedra and MO octahedra share edges and form a honeycomb open-framework with [Te MO] layers. The layers of [ MTeO] and [BiO] alternate and are connected along the c-axis by corner-sharing oxygen atoms to form the three-dimensional framework. The chiral compound BiGaTeO exhibits a powder second harmonic generation (SHG) response of ∼0.2 times that of potassium dihydrogen phosphate (KDP) and an absorption edge of 355 nm.

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