The sodium borosilicate glass doped with CuInS2 quantum dots was prepared by using both sol–gel and atmosphere control methods. The formation mechanism and the microstructure of the glass were examined using differential thermal analysis and thermal gravimeter, X‐ray powder diffraction, X‐ray photoelectron spectroscopy, transmission electron microscopy, scanning transmission electron microscopy, energy dispersive X‐ray spectra, high‐resolution transmission electron microscopy, and selected area electron diffraction. The results revealed that CuInS2 quantum dots in a tetragonal crystal system had formed uniformly in the glass, and the size distribution of these quantum dots generally ranged from 5 to 15 nm. In addition, Z‐scan technique was used to measure the third‐order optical nonlinearities of the glass. The results indicated that the glass has excellent third‐order optical nonlinearities, and thus will have potential applications in the field of nonlinear optics.