Phosphates with noncentrosymmetric (NCS) structures usually display short ultraviolet (UV) cut-off edges, but often exhibit weak powder second harmonic generation (SHG) intensities. Here we synthesized a NCS-phosphate, LiPbPO4, that achieves a desired balance between UV transparency, a cut-off edge of about 232 nm, and large SHG activity (about 3 x KDP). The three dimensional (3D) framework of LiPbPO4 consists of PO4 and LiO4 tetrahedra that are corner-shared, forming wide channels where lead cations reside. Local dipole moments for the PO4 and LiO4 tetrahedra as well as lead polyhedra in a unit cell were calculated. First-principles calculations have been performed for better understanding the structure-property relationships in LiPbPO4. In addition, to further explore spatial distribution of the electronic states dominating the NLO activity, the SHG density method was employed.