The effects of different laser pulse widths on laser-induced ionization imaging of microstructures embedded in transparent materials are investigated. It is shown that a femtosecond laser-induced ionization probe can detect the variation of elemental composition of the sample materials with a higher contrast ratio, whereas the ionization probe generated by picosecond laser pulses is more sensitive to the structural change inside optical materials, which can be well explained by the different roles of multiphoton ionization and avalanche ionization involved in material breakdown. These results also suggest that an optimum diagnosis could be obtained if well-selected laser parameters are employed in ultrafast laser ionization imaging.