With the rapid development of information technology, the demand for optoelectronic functional materials is increasing. Nonlinear optical materials are needed as basic materials in the optoelectronic industry, such as optical switches, optical communication, optical information processing, optical computers, laser technology, and so on. Therefore, nonlinear optical materials have received extensive attention in recent decades, but for nonlinear optical materials, the difficulty in their synthesis is the synthesis of noncentrosymmetric crystal structures. In this paper, three new compounds, namely Ag 2 (H 2 bpz) 2.5 (PF 6 )(OH)•H 2 O (1), Ag 2 (H 2 bpz) 2.5 (SbF 6 )(OH)•H 2 O (2), and Ag(H 2 bpz)(NO 3 )•H 2 O (3), have been synthesized and characterized by X-ray singlecrystal diffractometry; compounds 1 and 2 crystallize in a noncentrosymmetric space group. It is worth noting that the characterization results show that, through a simple hydrothermal reaction, we have successfully verified the feasibility of the theory of synthesizing noncentrosymmetric structures. In addition, compounds 1 and 2 synthesized by our simple method show second-harmonic generation, and it is phasematchable.