A series of xBi2O3-AlPO4-SiO2 glasses (0≤x≤0.15) were prepared by a sol-gel process. The local structures of glasses were investigated by magic angle spinning nuclei magnetic resonance (MAS NMR) and X-ray photoelectron spectroscopy (XPS). Based on the 27Al MAS NMR spectra. The results show that trere is Bi-O-Bi connectivity in all these glasses. In addition, the prepared glass is composed of AlPO4- and SiO2-nanodomains according to the results of 27Al{31P} REDOR, 31P{27Al} REAPDOR, 31P CT-DRENAR-BABA-xy16, and 29Si MAS NMR. The addition of Bi2O3 promotes the increase of AlPO4 clusters, forming the final phase, and Bi2O3 exists both in SiO2 and AlPO4 nanodomains.