We report a facile method to realize the fabrication of Na 2 O–B 2 O 3 –SiO 2 glass containing metallic Bi, Bi 2 O 3 and Bi 2 S 3 crystals. The microstructures of the glasses are investigated in detail by means of XRD, XPS, and TEM techniques. Furthermore, the third-order optical nonlinearities of the glasses are measured using femtosecond Z-scan technique at the wavelength of 800nm with a pulse width 200fs. Results show that the glasses exhibit the large third-order optical nonlinearities, and the third-order optical nonlinear susceptibility χ (3) of Na 2 O–B 2 O 3 –SiO 2 glass containing metallic Bi, Bi 2 O 3 and Bi 2 S 3 crystals are determined to be 5.81×10 −11 esu, 6.01×10 −11 esu, and 8.71×10 −10 esu, respectively. In particular, the third-order optical nonlinear absorption of the glasses are excellent, which have potential applications in the lasers as Q-switching elements and optical limiters.