Influence of CO2 laser bending on glass microstructure are studied by means of infrared (IR) spectra, X-ray powder diffraction (XRD) and scanning electron microscope (SEM). Test results show that slight phase separating tendency occurrs during the laser bending process, and the original triquetrous elements of ［BO3］ change into the tetrahedral elements of ［BO4］ by combining Na2O. Meanwhile, aggregation extent of Si increases and leads an enhancement of the Si—O bond intension. There is SiO2 crystal phase in the un-irradiated specimen with no obvious crystal phase in the irradiated one. And irregular globular grains of different dimension could be observed in the original specimen. On the contrast, the processed one presentes a character of uniform glass-phase.