Wide bandgap and strong second-order generation (SHG) effect are two crucial but contradictory conditions for practical nonlinear optical (NLO) materials. Herein, a new NLO crystal Pb2GaF2(SeO3)(2)Cl (I) containing novel functional (GaO3F3)(6-) octahedra is designed and synthesized by a rational band engineering strategy with aliovalent substitution. Benefiting from the removal of transition metal cations and the introduction of bridged F anions, I exhibits the widest bandgap among all reported phase-matchable NLO selenites. Meanwhile, a strong SHG response more than 4.5 times of KH2PO4 (KDP) is maintained. The dominate role of the (GaO3F3)(6-) groups to the enlarged bandgap in I are elucidated by first-principles studies.