Nonlinear optical (NLO) crystals have become a hot topic in chemical science and material physics, due to their essential role in laser technology, optical information, optoelectronics, and precision measurements. In this Perspective, we provide an overview of recent advances in second-order nonlinear optics, with a focus on two critical topics: second harmonic generation (SHG) and the bulk photovoltaic effect (BPVE). For SHG, we discuss recent progress in deep-ultraviolet (DUV) materials, highlighting their structural characteristics and nonlinear groups that contribute to their exceptional performance. For BPVE, we concentrate on the emerging field of low-dimensional materials, emphasizing their potential in a shift current. Additionally, we discuss the development of regulation approaches for NLO materials, which is vital for their practical application. Finally, we address the outlook for the field, including the challenges that must be overcome to further advance NLO materials research.