The scaffolder with phosphorus and selenium is very important structural unit. Their derivatives can be often used as potential antibacterial, antiviral, anticancer and antioxidant drugs. Furthermore, some of the selenides have been applied to the treatment of various diseases such as breast cancer, Alzheimer's disease, HIV infection.[1] Therefore, the synthesis method of containing P-Se bond has attracted much attention. Up to now, the synthesis method reported for constructing P-Se bond mainly include strong base catalysis, oxidation of strong oxidant, transition metal catalysis and photocatalysis.[2] Hence, it is of great significance to develop green, efficient and mild synthetic method to promote the construction of new P-Se bond. Herein, we have developed a simple and easy operation method to construct novel P-Se bond by weak base catalysis (Figure 1). A series of new pentacoordinate phosphorus compounds with excellent yield (up to 98%). The reaction requires no additional oxidants, and has good tolerance of functional groups and important application value in drug and organic synthesis.