A new nonlinear optical (NLO) material, Bi3TeBO9 (BTBO), is successfully grown from high temperature solution method. BTBO crystallizes in a polar space group of P63 with a framework structure composed of [Bi3O9] blocks, with TeO6 and BO3 interconnection. It is interesting that in the BTBO structure three types of NLO-active units, including stereochemically active lone pair cations (Bi3+ cations), second-order Jahn-Teller distorted octahedra (TeO6 octahedra) and π-orbital planar groups (BO3 groups), simultaneously exist. The additive contribution from these three types of groups results in an extremely large second harmonic generation (SHG) response in BTBO (about 20 times that of KDP), exhibiting the largest SHG effect among the known borate NLO materials. The enhancement of the nonlinear optical property is elucidated by the first-principles analysis.